PG M.sc. Chemistry 34431 Advanced Inorganic Chemistry

ALAGAPPA UNIVERSITY
[Accredited with ’A+’ Grade by NAAC (CGPA:3.64) in the Third Cycle

and Graded as Category–I University by MHRD-UGC]
(A State University Established by the Government of Tamilnadu)
KARAIKUDI – 630 003
DIRECTORATE OF DISTANCE EDUCATION
M.Sc.,
III-SEMESTER
34431
ADVANCED INORGANIC CHEMISTRY
Copy Right Reserved For Private use only

Author:
Dr. N. Sengottuvelan
Assistant Professor,
Directorate of Distance Education
Department of Industrial Chemistry,
Alagappa University,
Karaikudi -3
“The Copyright shall be vested with Alagappa University”
All rights reserved. No part of this publication which is material protected by this copyright notice
may be reproduced or transmitted or utilized or stored in any form or by any means now known or
hereinafter invented, electronic, digital or mechanical, including photocopying, scanning, recording
or by any information storage or retrieval system, without prior written permission from the
Alagappa University, Karaikudi, Tamil Nadu.
Reviewer:
Dr. AN. Senthilkumar,
Assistant Professor
Alagappa Govt. Arts College,
Karaikudi -3.
SYLLABI-BOOK MAPPING TABLE
ADVANCED INORGANIC CHEMISTRY
Syllabi Mapping in Book
BLOCK- I COORDINATION CHEMISTRY
Unit-1: Stability of coordination compounds Pages 1 - 12
Stability constants
Stepwise and overall formation constants
pH metric, polarographic and Spectrophotometric methods of determining stability
constants Chelate effect.
Unit-2: Kinetics and mechanisms of coordination compounds Pages 13 -34
Kinetics and mechanisms of reactions in solution
Labile and inert complexes
Ligand displacement reactions
Hydrolysis, anation, aquation in octahedral complexes
Substitution reactions in square planar complexes
Trans effect –
Electron transfer reactions
Unit-3: Complementary and non-complementary reactions
Pages 35 - 46
Inner sphere and outer sphere processes
isomerisation and racemisation
Template effect and
synthesis of macrocyclic ligands.
BLOCK 2 SPECTRAL PROPERTIES OF COMPLEXES, SPINELS, CAGES,
CLUSTERS AND BORANES Pages 47–63
Unit -4 : Spectral properties of complexes
Electronic spectra of coordination compounds
selection rules, band intensities and band widths
Term state for d ions in Octahedral complexes
energy level diagrams of Orgel and Tanabe - Sugano diagram
Unit -5 : Spinels Pages 64 -75
Spinels
Normal and inverse types
Site preferences in spinnels.andperovskite structures.
Unit -6: Cages and metal clusters Pages 76 - 82
Inorganic chains - rings
Cages, Metal clusters
Dinuclear clusters
Trinuclear clusters
Tetranuclear clusters
Hexanuclear cluster.
Unit -7: Boranes
Boranes: Pages 83-98
Structure and bonding in polyhedral boranes
Carboranes,
Styx notation
Wade’s rule;
Electron count in polyhedral boranes, isolobal analogy.
BLOCK-3 ORGANOMETALLIC CHEMISTRY

Unit-8: Definition of Organometallics
M-C – bond
Low oxidation state of metal – explanation Pages 99 - 112
synthesis and structure of metal alkyls and aryls
Olefin and acetylene complexes
Dewar-Chatt approach to bonding in olefins
Unit-9: Metallocenes Pages 113 - 122
Metallocenes
Structure
Comparison of ferrocene with other metallocenes with respect to their reactivity,
Stability etc
preparation of ferrocene –properties
Fluxional molecules.
Unit-10: Metal carbonyl Pages 123 - 137
Metal carbonyl complexes
Synthesis - structure and reactions of metal carbonyls
Metal carbonyl anions
Metal carbonyl hydrides - metal carbonyl halides
Metal carbonyl clusters - metal nitrosyls.
Unit -11: Catalysis involving organometallics Pages 138 - 156
Oxidative addition and reductive elimination,
Hydrogenation
Hydroformylation,
Monsanto process,
Isomerisation and
Ziegler-Natta polymerization.
Unit-12: Metalloporphyrins and Metalloenzymes Pages 157- 178
Chlorophyll
Hemoglobin and myoglobin structure and function of hemoglobin
Cytochromes,
Enzyme action-inhibition and restoration.
Carboxy peptidase-A,
Vitamin B12 and B12 coenzymes.
Copper containing oxidase.
Unit-13: non-heme iron proteins Pages 179 - 185
Rubridoxin
Ferrodoxins – HIPIP,
Fixation of nitrogen - in vivo systems
Unit-14: Metal ions in biology Pages 186 - 196
Alkali and alkaline earth metal ions in biology
Sodium ion pump.
Metal poisons and
Chelating agents in medicine.
CONTENTS
Unit-1: Stability of coordination compounds
1.0 Introduction 1 - 12
1.1 Objectives
1.2 Stability constants
1.3 Stepwise and overall formation constants
1.4 Determining stability constants
1.4.1 pH metric method
1.4.2 Spectrophotometric method
1.5 Chelate effect
1.6 Check your progress questions
1.7 Answers to check your progress questions
1.8 Summary
1.9 Keywords
1.10 Self-assessment questions and exercises
1.11 Further readings
Unit- 2: Kinetics and Mechanisms of Coordination Compounds 13 - 34
2.0 Introduction
2.1 Objectives
2.2 Kinetics and mechanisms of reactions in solution
2.2.1 Labile complex & inert complex
2.2.2 Factors affecting the labile/inert nature of complexes
2.3 Ligand displacement reactions
2.3.1 Hydrolysis in octahedral complexes
2.3.2 Anation in octahedral complexes
2.3.3 Aquation in octahedral complexes
2.4 Substitution in square planar complexes
2.4.1 Trans effect
2.5 Electron transfer reactions
2.6 Check Your Progress
2.8 Summary
2.9 Keywords
Unit- 3: Complementary AndNon-Complementary Reactions 35 - 46
3.0 Introduction
3.1 Objectives
3.2 Complementary and Non- Complementary reactions
3.3 The classification of redox reactions
3.4 Outer-sphere mechanism
3.5 Inner-sphere mechanism
3.6 Isomerization and racemization
3.7 Template effect and synthesis of macrocyclic ligands
3.10 Summary
3.11 Keywords
BLOCK 2 SPECTRAL PROPERTIES OF COMPLEXES, SPINELS, CAGES,
CLUSTERS AND BORANES
Unit -4: Spectral properties of complexes 47 – 63

4.0 Introduction
4.1 Objectives
4.2 Types of spectra
4.2.1 Electronic absorption spectroscopy principles
4.2.2 Russel-Saunders or L-S coupling
4.2.3 Term state for d ions in Octahedral complexes
4.2.4 Number of microstates
4.2.5 Selection rule
4.2.6 Mechanism of breakdown of selection rules
4.3 Splitting of energy states
4.3.1 Energy level diagram
4.3.2 Orgeldiagrams
4.3.3 Inter-electronic repulsion parameters
4.3.4 Racah parameters
4.3.5 Tanabe –Sugano diagrams
4.6 Summary
4.7 Keywords
Unit -5: Spinels 64- 75
5.0 Introduction
5.1 Objective
5.2 Classification of spinels
5.3 Normal Spinels
5.4 Inverse Spinels
5.5 Perovoskite Structure
5.6 Answer to check your progress
5.7 Summary
5.8 Keywords
5.9 Self Assessment and exercise
5.10 Further Reading
UNIT -6: CAGES AND CLUSTERS 76-82
6.0 Introduction
6.1 Objectives
6.2 Classification of metal clusters
6.3 Criteria for metal Clusters
6.4 Types of metal clusters
6.4.1 Dinuclear Clusters
6.4.2 Trinuclear Clusters
6.4.3 Tetranuclear Clusters
6.4.4 Hexanuclear Clusters
6.5 Answers to check your progress
6.6 Summary
6.7 Key words
6.9 Further Reading
Unit -7: Boranes 83 -98
7.0 Introduction
7.1 Objectives
7.2 Boranes & Higher Boranes
7.2.1 Nomenclature of boranes
7.2.2 Classification
7.3.3 Synthesis
7.3 Carboranes
7.3.1 Nomenclature
7.3.2 Preparation
7.4 Wade’s rules
7.5 STYX notation
7.5.1 Predicting structures of cluster compounds
7.5.2 4n rules
7.5.3 5n rules
7.5.4 6n rules
7.5.5 Isolobal vertex units
7.5.6 Isolobal Analogy
7.6 Check your progress question
7.7 Answers to Check Your Progress Questions
7.8 Summary
7.9 Keywords
7.10 Self-Assessment Questions and Exercises
7.11 Further Readings
BLOCK-3 ORGANOMETALLIC CHEMISTRY 99 - 112
Unit-8: Definition of Organometallics
8.0 Introduction
8.1 Objectives
8.2 Synthesis of Metal Alkyl Complexes
8.2.1 Reactions of Metal alkyls
8.3 Metal alkene complexes
8.4 Dewar-Chatt approach to bonding in olefins
8.5 Metal – alkyne complexes
8.5.1 Reactivity of Alkyne Complexes
8.6 Metal – AreneComplexs
8.9 Summary
8.10 Keywords
Unit-9: Metallocenes 113 - 122
9.0 Introduction
9.1 Objective
9.2 Comparison of ferrocene with other metallocenes with respect to their reactivity
9.3 Molecular orbital diagram of Ferrocene
9.4 Preparation of Ferrocene (5–C5H5)2Fe
9.5 Properties of Ferrocene
9.6 Fluxional Molecules
9.9 Summary
9.10 Keywords
9.11 Self assessment question and exercise
Unit-10: Metal carbonyl 123 - 137
10.0 Introduction
10.1 Objectives
10.2 Metal Carbonyls
10.2.2 Preparation and Properties of metal carbonyls
10.2.3 Structure M-C bond
10.2.4 Vibrational Spectra
10.3 Metal Carbonylate Anions
10.4 Metal Carbonyl Hydrides
10.5 Metal nitrosyl complexes
10.8 Summary
10.9 Keywords
Unit -11: Catalysis involving organometallic 138 - 156
11.0 Introduction
11.1 Objectives
11.2 Oxidative addition
11.3 Reductive elimination
11.4 Hydrogenation
11.5 Hydroformylation
11.6 Monsando process
11.7 Zieglar Natta Polymerization
11.8 Isomerisation
11.11 Summary
11.12 Keywords
UNIT- 12 Metalloporphyrins and Metalloenzymes 157- 178
12.0 Introduction
12.1 Objectives
12.2 Chlorophyll
12.2.1 Chemical structure of Chlorophyll
12.2.2 Function of chlorophyll
12.2.3 Mechanism of Photosynthesis
12.3 Structure and function of Hemoglobin (Hb) and myoglobin (Mb)
12.3.1 Mode of Oxygen transport
12.3.2 Mechanism of oxygenation in Hb and Mb
12.3.3 Cooperativity
12.4 Cytochromes
12.5 Enzymes
12.5.1 Enzyme action
12.5.2 Inhibition
12.6 Vitamin B12 and B12 coenzymes
12.6.1 Reactions of Vitamin B12
12.6.2 Function
12.7 Carboxypeptidase – A
12.7.1 Structure
12.7.2 Mechanism of catalysis
12.8 Copper containing oxidases
12.8.1 Structure
12.8.2 Catalytic Mechanism
12.10 Summary
12.11 Keywords
Unit-13: Non-heme iron proteins 179 - 185
13.0 Introduction
13.1 Objective
13.2 Structural motifs
(13.2.1) Rubredoxins[1Fe-0S] proteins
(13.2.2 )Two-Iron Ferredoxins [2Fe-2S] proteins
(13.2.3) 3Fe–4S clusters
(13.2.4) 4Fe–4S clusters
13.3 Nitrogen Fixation
13.3.1 In Vivo Nitrogen fixation
13.4. Check your progress question
13.6 Keywords
13.7 Summary
UNIT-14: Metal ions in biology 186-196

14.0 Introduction
14.1 Objective
14.2 Alkali and Alkaline earth metals in biology
14.2.1 Biological importance of Sodium
14.2.2 Biological Importance of Magnesium
14.2.3 Biological Importance of Potassium
14.2.4 Biological Importance of Calcium
14.3 Sodium ion pump
14.3.1 Steps involved in the Sodium-Potassium Pump (Na+-K+ pump)
14.3.2 Details of mechanism
14.4 Metal Ion Poisoning
14.4.1 Industrial Sources
14.4.2 Metallotherapy
14.4.3 Automobile Engines
14.4.4 Foods and Plants
14.5 Chelating agents in medicine
14.5.1 Synergistic Chelation Therapy
14.5.2 Mixed Ligand Chelation Therapy
14.5.3 Chelate Therapy
14. 8 Summary
14.9 Keywords
14.10 self assessment question and exercise
Model Question Paper 197
BLOCK- 1 COORDINATION CHEMISTRY Stability of Coordination
Compounds
UNIT-1 STABILITY OF COORDINATION COMPOUNDS

Structure
1.0 Introduction
1.1 Objectives
1.2 Stability constants
NOTES
1.3 Stepwise and overall formation constants
1.4 Determining stability constants
1.4.1 pH metric method
1.4.2 Spectrophotometric method
1.5 Chelate effect
1.8 Summary
1.9 Keywords
1.0 Introduction
When the term stability is applied to coordination compounds (metal
complexes), there can be two interpretationsw.r.t thermodynamic and kinetics.
Thermodynamic stability refers to the change in free energy on going from
reactants to products, i.e., ∆G for the reaction. Recall that ∆G=∆H-T∆S = -
RTlnK, where ∆H is the enthalpy, ∆S the entropy T the absolute temperature
and K is the equilibrium constant for the reaction. Kinetic stability refers to
reactivity, generally ligand substitution. When assessing chemical reactions we
need to consider both thermodynamic and kineticaspects because although a
reaction may be thermodynamically feasible, there might bekinetic constraints.
In this section we are going to focus on the formation constants, stepwise
formation constants with their methods of determination and chelate effect.
1.1 Objectives
After going through this unit, you will be able to:
 Understand about the stability constants
 Understand the methods of determining the stability constants
 Appreciate the chelation effect
1.2 Stability Constants
When a metal ion in aqueous solutions interacts with a neutral and
monodentate ligand, the system at the equilibrium may be described by the
equation
[M(H2O)x]n+ + L [M(H2O)x-1L]n+ + H2O
Where x is the number of water molecules in the aqua complexes and n is the
oxidation number of the metal ion. When L is an anionic ligand, the ligand
binding equilibrium would be :
[M(H2O)x]n+ + L- [M(H2O)x-1L](n-1)+ + H2O

1
Self-Instructional Material
We may write the equilibrium reaction in a simplified and generalized form
Stability of Coordination
Compounds without referring to the number of coordinated water molecules as follows:
M+L ML
The equilibrium constant of the reaction is given by the equation given below
Kf = [ML]/[M]*[L]
Kf is called formation constant of the complex.
NOTES Note that here we assume that the concentration of H 2O is constant in a dilute
solution of the metal complex and it is incorporated into the above Kfequation.
If a large amount of the complex is formed then the equilibrium concentrations
[ML] is larger than the product of [M]*[L], then Kfis more than 1.0. Such a
situation would arise when the ligand L binds to the metal more tightly than
H2O. Thus a large value of Kfmerely indicates that L is a stronger ligand than
H2O. Similarly, when Kfis less than 1.0, the L is a weaker ligand than H2O. The
magnitude of the formation constant is the measure of stability of a coordination
complex.In a thermodynamic sense,the formation constants are also called
Stability constants.In studying the formation of complexes in solution, two
types of stability of complexes are found
1. Thermodynamic Stability
It is a measure of the extent of which the complex will form or will be
transformed into another species under certain conditions, when the system has
reached in equilibrium. This type of stabilities are dealt with metal-ligand bond
energies, stability constant etc.,
2. Kinetic Stability
IT refers to the rate with which transformation leading to the attainment
of equilibrium will occur. When we are interested in kinetic stability for
complex ions in solutions are dealt with rates and mechanism of chemical
reactions. These reactions may be substitution, isomerisation, recemisation and
electron or group transfer reactions. In the kinetic sense, it is more proper to call
the complexes inert or labile complex rather than stable or unstable complex.
The complexes in which the ligands are rapidly replaced by others are called
labile complexes, while those in which substitution occurs slowly are called
inert complexes.
1.3 Stepwise and Overall Formation Constants
According to J. Bjerrum (1941) the formation of a complex in solution
proceeds by the stepwise addition of the ligands to the metal ion. Thus the
formation of the complex MLn may be supposed to take place by the following
n consecutive steps.
where M = central metal cation
L = monodentate ligand
n = maximum co-ordination number for the metal ion M for
the ligand
M+L ML
( ML)
K1 
[ M ][ L]
2
Compounds
ML + L ML2 K 2  ( ML2 )
[ ML][ L]
ML2 + L ( ML3 )
ML3 K3 
[ ML 2][ L]
Thus MLn-1 + L MLn ( MLn )
Kn  NOTES
[ MLn  1][ L ]
The equilibrium constants, K1, K2, K3, ..........Kn are called stepwise stability
constants.
The formation of the complex MLn may also be expressed by the following
steps and equilibrium constants.
M + L  ML,
B1 ( ML)

[ M ][ L]
M +2L  ML2,  2 

B2 ( ML2 )
[ M ][ L]2
Thus M + nL  MLn,  n = n 

Bn ( MLn)
n
[ M ][ L]
The equilibrium constants,  1,  2,  3, .......... are called stepwise formation

constants.  n is called as nth overall (or cumulative) formation constant or
overall stability constants. The higher the value of stability constant (k) for a
complex ion, the greater will be its stability. Alternatively 1/k values sometimes
are called instability constant.
Stepwise and cumulative stability constants are also expressed as
log10K1, log10K2................log10Kn and log10n respectively.
Relationship between n and K1, K2, K3, ..........Kn
K's and's are related to one another as said
Consider for example, the expression for  3 is:-
( ML3 )
3 
[ M ][ L]3
On multiplying both numerator and denominator by [ML] [ML2] and on
rearranging we get:
[ ML3 ] [ ML][ML2 ]
3  
[ M ][ L]3 [ ML][ML2 ]
[ ML ] [ ML2 ] [ ML3 ]
  
[ M ][ L] [ ML][ L] [ ML2 ][ L]
= K1 x K2 x K3
Thus
n = n 
[ ML ]

[ ML2 ]
.............
[ MLn ]
[ M ][ L] [ ML][ L] [ MLn 1 ][ L]
= K1 x K2..........Kn
Or
3
nn
Compounds
n  K
n 1
n
From above relation, it is clear that the overall stability constant n is

equal to the product of the successive (i.e. stepwise) stability constants, K1, K2,
K3, ..........Kn. This in other words means that the value of stability constants for
NOTES
a given complex is actually made up of a number of stepwise stability constants.
Factors Affecting Stability Constant (K)
Metal: The nature of the metal ions influences the stability of the complex as
follows
 Stability (or stability constant) increases with decreasing size of metal
ion. K generally varies with radius of metal ion r as 1/r.
 Stability constants for a complex increase with the charge of the central
ion. The K for the Fe(II) complexes will be less then the K for the
corresponding Fe(III) complexes.
 The ions with high polarizability give complexes with higher stability
constants. Thus Cu(I) complexes have higher K values than the similar
sized Na(I) complexes, similarly of Ca(II) and Cd(II) or Al (III) and
Ga(III) the former have low K values for the complex formation.
 Electronegativity increases the polarizing power and the ions with higher
electronegativity give stable complexes.
 Ionization Energies: The electronegativity, covalent nature and ionic
radii can be related to the ionization energies of the atoms. It is found
that the stability constants for the metal complexes with a ligand
increases with the ionization energies of the metallic species.
Observations of Bjerrum Niecilson and others show that although most
of the metals of the periodic table form complexes, this tendency is the most
with transition metals. The reason being that the chelate effect is almost an
entropy effect for the metal ions of nontransitional group, while for the
transitions metals it is partly an enthalpy effect which increases the crystal field
strength. The increase in crystal field strength increases the points of attachment
of the ligand to the metal ion imparting greater chelating tendency to the latter.
Mellor and Maley have shown that the stabilities of the complexes of
bivalent metal ions follow the order: Pd > Cu > Ni > Pb > Co > Zn > Cd > Fe >
Mn > Mg irrespective of the nature of the ligand. Irving and Williams from the
analysis of the data on stability constants of transition metal ions, found that the
order holds good.
Mn(II) < Fe(II) < Co(II) < Ni(II) < Cu(II) > Zn(II),
This order according to them follows logically from a consideration of
the reciprocal of ionic radius and second ionization potential of the metal, and is
known as 'Natural Order of Stability.
Univalent ions have not been extensively studied but data on the
complexes of the univalent ions with dibenzol methanate ion shows the order of
the stability as:
Ag > Tl > Li > K > Rb > Cs
4
Factors Related With Ligands Stability of Coordination
The properties of the ligands which affect the stability of the metal Compounds
complexes are as under:

Basicity of the ligands: The greater is the Lewis base strength, higher is
expected to be the stability constant of the complex.
Dipole moment and polarizability of the ligands: Due to the greater
electrostatic interactions between the metal ion and the ligands, polarity and
NOTES
polarizability of ligand results in higher K for the complexes.
(ML) π- back bonding always increases the stability of the complex.
Steric factor: It plays an important role in determining the stability constants
for the complexes.
Ring Formation and Size of the Ring
Ring complexes or chelates are very stable due to reduced strain. The
number of ring formed the size of the rings and stabilizing or interfering
resonance interactions are determined by the structure of the chelating agent.
Schwarzenbach and Co-workers have observed that there is a decrease in
chelate stability with the increase in ring size. The stability of a five membered
ring is not mainly due to entropy but rather to the enthalpy of formation; Further
the stability increases with the increase in the number of rings in the molecule:
M(en) < M(trien) < M(EDTA).
(one ring) (two rings) (five rings)
Steric Effect: Steric hindrance can influence stability in many ways, e.g.
(i) Metal-ligand bonds are weakened due to the presence of bulky group
near the coordinating site.
(ii) The substituting group prevents the ligand from assuming the planar
configuration and hence introduce strain in the metal-donor bond.
(iii) Steric hinderacne is also due to strained structure of the chelated ring,
since it breaks the usual linear configuration of the complexes.
From the study of the copper complexes of substituted malonic acids
Riley concluded that ethyl and propyl groups had a larger effect then methyl in
reducing the stability.
Chelate Effect
The chief factor responsible for the stability of the chelate ring is the
entropy change which can be viewed statistically or as probability factor.
Considering the electronic effect of the donor atom to be the same in the
monodentate and the bidentatc ligands, it can be seen that the dissociation of a
monodentate from a complex will be higher than that in the chelating bidentate.
The dissociation of the M-L bond in monodentate will release the ligand
completely from the coordination sphere of the metal, so that it can be easily
swept off by the solvent. But the dissociation of one M-L bond for the bidenate
ligand does not release the ligand completely (for which simultaneous
dissociation at both ends is required). Hence the stability constant for metal
chelate must be higher. Consider the equilibrium reactions
[Co(NH3)6]3+ + 3en  [Co(en)3]3+ + 6NH3
Assuming that (i) Co-N bond strength in the two complexes is same (the
f value of ammonia and ethylendiamine are within 3%), and (ii) the entropy
5
changes due to structure making and structure breaking are negligible due to the
Compounds similar size of the complexes, it can be seen that the S o will increase for the
reaction as the number of moles of the products are more than those for the
reactants. This will help the reaction to go to the right.
1.4 Determining Stability Constants
In order to determine the values of n formation constants, n + 2 independent
NOTES concentration measurements are needed. These can be used to obtain the
concentration of the n species, ML1 ML2 ---- MLn and also those of M & L. We
should know the quantities of M and L used in the experiment. This means that
n additional pieces of information are needed. If it is certain that only one
complex of known empirical formula is formed, then a measurement of the
concentration of the uncomplexed M or L is sufficient to determine the
formation constant. This measurement can be made in many ways, by
polarographic or emf measurements (if a suitable reversible electrode exists), by
pH measurements (if the acid dissociation constant of HL is known) and by
many other techniques. Various experimental methods are used to determine the
composition and stability constants of the complexes.
1. Measurement of colligative properties
2. Optical methods (spectrophotometric study of systems with two & three
or more components)
3. NMR & ESR methods
4. Calorimetry
5. Determination of equilibrium constants via kinetic measurements
6. Extraction methods
7. Solubility studies
8. Study of ion exchange Equilibria
9. Potentiometry & pH-metric equilibrium studies
10. Polarography and
Other methods such as measurement of conductivity, polarimetry, Infrared
spectrophotometry, Raman spectrophotometry, equilibrium study of metal
complexes of anionic ligands, polarographic diffusion current,
chronopotentiometry, cyclic voltammetry, gas chromatography, density
measurement, magnetic susceptibility measurement, emission titration,
measurement of self-diffusion coefficient, positronium annihilation and pressure
measurement in the case of gaseous ligands are also employed. The possibilities
for the application of other methods are limited as they each relate only to a
well-defined group of equilibrium systems.
1.4.1 pHMetric Method
Bjerrum's Method
It is a potentiometric method for determining the stability constant of a
complex. Although Bjerrum applied the method primarily to the binding of
simple molecules or negative ions to positive metal ions. It may be used with
equal success with chelating agents. The theoretical relationship outlined by
Bjerrum are not restricted to complex formation but may be applied to any
equilibrium process regardless of the nature of the interacting substances. Thus,
it has been used with success on acid base, and redox equilibria. Although the
6
reactions to be considered involve ions that are more or less completely Stability of Coordination
hydrated, rather than the simple ions, but this fact does not affect the validity of Compounds
the conclusions, provided the activity of the water is maintained constant.

Formation or dissociation of a complex ion for molecule in the solution
always takes place in several steps, which can be easily determined by
measuring pH in this method.
Experimental Determination of Stability Constant by Bjerrum's Method
NOTES
This is a potentiometric method. When the lignad is a weak base or acid,
competition between hydrogen ion and metal ions for ligand can be used to the
determination of the formation constant.
Let us consider the equilibrium in which an acid and metal ions are
added to a basic ligand in solution. Thus the following equation are obtained:
[ HL  ]

L + H+  HL+, Ka = [ L][H ]
Ka
Basic Ligand Acid

[ ML ]

L + M+  ML+, KF = [L][M ]
KF
Basic Ligand Metal ion

Here Ka and KF are the acid association constant of the ligand and
formation constant respectively.
Now if CH, CM and CL are the total amounts in moles/litre of acid (H+) ,
metal (m+) and basic ligand (L), we have
CH = [H+] + [HL+]
CL = [L] + [ML+] + [HL+]
CM= [M+] + [ML+]
Solving the last three equations given above and using the acid
association constant of the ligand, Ka. Then we get
CH [H  ]
[ML+] = CL - CH + [H+] 
Ka [ H  ]
+ +
[M ] = Cm - [ML ]
CH [H  ]
L
Ka [ H  ]
Thus on putting the values of [ML+], [M+] and [L] from the above
equation in
[ML ]
K1 
[M  ][L]
The value of K1 can be calculated. For the determination of [ML+], [M+]
and [L], the values of C H, CL, Cm, Ka and [H+], is generally determined
potentiometrically using a pH meter.
In order to get better results, the ligand must be a medium weak acid or
base and the formation constant, K1, should be within a factor of 105 of the
value of the acid association constant of the ligand, Ka.
7
1.4.2 Spectrophotometry Measurements
Compounds The basic principle of the spectrophotometric technique is the
measurement of interactions between radiation energy and electrons of the
substance. This is used in estimation of the concentration of metal ion in liquid
solution. One of the most spectacular effects of complex formation is the change
of spectral properties. Complexes absorb the light due to
NOTES (1) The excitation of electrons of both the metal ion and the ligand is influenced
by their interaction.
(2) The electrons of transition metal ions are easily excited and absorb in the
visible region.
(3) The electron system of non-transition metal ions and ligands are stable
requiring greater amount of energy, so absorb in the ultraviolet region.
(4) A charge transfer from ligand to metal ion may occur on irradiation due to
interaction of central ion and ligand. This causes in the charge transfer spectra to
occur in the visible and near ultraviolet region. The following points are to be
noted during measurements.
Beer's Law: If a given species in solution absorbs light and obeys Beer's law,
then it is possible to find out its concentration. This law can be regarded as
idealized behaviour of the species towards strictly monochromatic radiation.
The formation constant of a complex can be calculated by taking known amount
of metal and ligand and measuring the optical density of the metal, ligand and
the metal-ligand mixture separately.
Selection of Wavelength: Firstly, it is necessary to select the wavelength at
which complex species has a greater absorption to that of free metal ion or free
ligand. For this, spectra of metal-ligand mixture is compared with the spectra of
free metal ion and free ligand. It is also important that at a wavelength selected,
only one complex species should predominantly absorb light. As nitrate ions
have no absorbance in the spectral range of 250 nm to 1800 nm, metal nitrate
solution will show absorption of light by metal ions alone.
Selection of pH: For selecting the optimum pH for studying complex formation,
a preliminary study of spectra of(i) The metal ion (ii) The ligand ion and (iii)
Metal ion + ligand,has to be made over a large range of pH up to the pH of
hydrolysis. If more than one complex is formed at different pH conditions, their
existence can be decided by this type of study. The pH at which absorption due
to complex is far greater than that of metal ion or the ligand alone, is selected
for the study of that species. As the complex formation is the function of pH; it
should be kept constant for that system. Similarly, by adding appropriate
volume of potassium nitrate, ionic strength is maintained constant throughout.
pH can be maintained constant by using a proper buffer, but buffer should not
interfere with the complex formation and should not absorb itself at the
maximum wavelength of absorption of complex species. For complexes which
show different colour with a change in pH, a plot of optical density against
wavelength over a wide range of pH gives a number of curves representing
absorption spectra. The points at which the curves corresponding to a number of
solutions having equal formal concentration of metal and ligand intercept are
called the isobestic points.
8
The Composition of the Complexes Stability of Coordination
Before determining the stability constants of a given complex; it is necessary to Compounds
ascertain the number of ligand groups attached to the metal ion. The
composition of the complex can be determined by Job's method of continuous
variation.
Job's Method of Continuous Variation
It consists of mixing equinormal solutions of metal and ligand in varying
NOTES
proportion but keeping the total concentration of the metal plus the ligand
constant in the mixtures. The absorbance of these mixtures is measured at a
suitable wavelength. If x mole/litre of L are added to (1-x) mole/litre of M and if
C1, C2 and C3 are the equilibrium concentrations in mole/litre of M, L and ML n
respectively, then,
C1 = (1-x) - C3
C2 =(x-nC3)
C3 =C1 C2n
'n' is the number of ligands attached to a metal ion which can be easily
determined from the position of the maximum or minimum in the graph. If the
metal ion and the ligand are colourless, but the complex species is coloured,
then there will be maximum at the composition of the complex in the plots of
absorbance versus composition. Job's method is ordinarily applicable to systems
in which only one complex is present.
Calculations of Stability Constants
The stability constant of a complex can be determined from Job's curve by the
following two methods:
From extinction coefficient data
Optical density of solution (M : L = 1 : 25) can be considered to be due to the
complex. The concentration of complex may be taken equal to that of the metal
ions as all the metal ions are utilized in forming the complex. From optical
density, one may determine the extinction coefficient of the complex by using
Beer's law. From this value, the concentration and stability constants of the
complex in various mixtures can be calculated.
Method of Corresponding Solutions
A solution (M : L = 1 : 1) can be diluted at constant ionic strength, until
solutions are obtained having the same optical densities. In this way, pairs of
solutions may be prepared which have the same optical density [equal
concentration of the complex] but different total concentration of the metal and
ligand.
Suppose D1 and D2 are the concentrations of [ML1] and [ML2] respectively
obtained from the observed solutions (i) and (ii). Now; as D1=D2, we can write
[ML1] = [ML2] and the formation constant k' is given by
[ML1] [ML2]
k' = =
[M]1[L]1 [M]2[L]2
Since, [ML1] = [ML2] = [ML]
9
[ML] [ML]
Compounds
k' = =
TM1 - [ML] TL1 - [ML] TM2 - [ML] TL2 - [ML]
Where, TMI and TLI are the concentrations of total metal and total ligand
respectively in solution (i) and TM2 and TL2 are the concentrations of total metal
and total ligand respectively in solution (ii). As the values of T M and TL are
NOTES
known, the value of k' can be calculated.
The extent of complex formation is characterised by the ligand number n, given
as
TL - [L]
n=
TM
Where TL is the concentration of ligand in all forms, [L] is the concentration of
free chelating species and TM is the total concentration of metal ion (bound or
free).
1.5 Chelate Effect
The chelate effect causes polydentate complexes to be
thermodynamically more stable than their monodentate counterparts.
Substitution for a chelated ligand is generally a slower reaction than that for a
similar monodentate ligand. Explanations for this effect centre on two factors.
First, the ∆H associated with removal of the first bound atom is larger than for a
related monodentate ligand. If this atom does separate from the metal centre, its
kinetic barrier for subsequent reattachment is lower than for a related
monodentate ligand since the former remains in close proximity to the metal
centre.
Consider the general scheme below:
The first dissociation (1) is expected to be slower than a similar

dissociation of ammonia, because the ethylenediamine ligand must bend and
rotate to move the free amine away from the metal. The reverse reaction
associated with the first dissociation is fast. Indeed, the uncoordinated nitrogen
10
is held near the metal by the rest of the ligand, making reattachment more likely. Stability of Coordination
This kinetic chelate effect dramatically reduces aquation reaction rates. Compounds

1. What is meant by stepwise formation constant?
2. What are the different methods used to determine stability constants?
3. Explain chelate effect.
4. Give the expression of the real stability constant? NOTES
1.7 Answers To Check Your Progress Questions
1.When more than one coordinated water molecule of [M (H 2O)x]n+ is replaced
by the ligand L, then we have to consider several steps. At each step we need to
consider an equilibrium constant called the stepwise formation constant (or
stepwise stability constant).
2. Various experimental methods are used to determine the composition and
stability constants of the complexes; these are
 Measurement of colligative properties
 Optical methods (spectrophotometric study of systems with two & three
or more components)
 NMR & ESR methods
 Calorimetry
 Determination of equilibrium constants via kinetic measurements
 Extraction methods
 Solubility studies
 Study of ion exchange Equilibria
 Potentiometry & pH-metric equilibrium studies
 Polarography and
 Other methods
3. When a ligand attaches to the metal ion in a manner that forms a ring, then
the metal- ligand association is found to be more stable. In other words, we can
say that complexes containing chelate rings are more stable than complexes
without rings. This is known as the chelate effect.
1.8 Summary
 Inorganic chemists frequently use stability constants, sometimes called
formation constants, as indicators of bonding strength. These are
equilibrium constants for reactions that form coordination complexes.
 When more than one coordinated water molecule of [M (H 2O)x]n+ is
replaced by the ligand L, then we have to consider several steps. At each
step we need to consider an equilibrium constant called the stepwise
formation constant (or stepwise stability constant).
 Various experimental methods are used to determine the composition
and stability constants of the complexes; these are pH metric,
spectrophotometric, polarographic, etc.
 For determining the stability constants of a given complex through
spectrophotometric method; it is necessary to ascertain the number of
ligand groups attached to the metal ion. The composition of the complex
can be determined by Job's method of continuous variation.
11
 The chelate effect causes polydentate complexes to be
Compounds thermodynamically more stable than their monodentate
counterparts.Complexes containing chelate rings are more stable than
complexes without rings.
1.9 Keywords
Chelate Effect: Complexes containing chelate rings are more stable than
NOTES complexes without rings and is known as chelate effect.
Bjerrum's Method: It is a potentiometric method for determining the stability
constant for complex formation.
Job's method of continuous variation: The composition of the complex can be
determined by Job's method of continuous variation.
1. Explain in detail about the formation constants.
2. Discuss in detail about stepwise formation constants.
3. Give the detailed picture of spectrophotometric method for determining
stability constants
4. Explain about chelate effect with an example.
1. Huheey, J.E., E.A. Keiter and R.L. Keiter. 2002. Inorganic Chemistry:
Principles of Structure and Reactivity, 4th Edition. New York:
HarperCollins Publishers.
2. Gary L. Miessler., Paul J. Fischer., Donald A. Tarr. Inorganic Chemistry,
5th ed : Pearson
3. Shriver and Atkins., Inorganic Chemistry, 5th ed : W. H. Freeman and
Company New York.
12
UNIT-II KINETICS AND MECHANISMS
Complementary and Non-
OF COORDINATION COMPOUNDS ComplentaryRreactions
Structure
2.0 Introduction
2.1 Objectives
2.2 Kinetics and mechanisms of reactions in solution NOTES
2.2.1 Labile complex & inert complex
2.3 Ligand displacement reactions
2.3.1 Hydrolysis in octahedral complexes
2.3.2 Anation in octahedral complexes
2.3.3 Aquation in octahedral complexes
2.4 Substitution in square planar complexes
2.4.1 Trans effect
2.5 Electron transfer reactions
2.8 Summary
2.9 Keywords
2.0 Introduction
Reactions of coordination compounds are understood using the same
fundamental concepts applied to all reactions. The chemistry of
coordination compounds is distinctive because (1) the complexes have a
relatively large diversity of geometries and more possibilities for
rearrangement, and (2) metal atoms impose significant variability on the
reactivity of their complexes.Reactions of coordination complexes can be
divided into (1) substitution at the metal centre, (2) oxidation–reduction,
and (3) reactions of the ligands that do not change the attachments to the
metal centre. In this context, we discuss in detail about the labile and inert
complexes, different types of ligand displacement reactions in octahedral
complexes, mechanisms behind the substitution reactions in square planar
complexes, Trans effect and the electron transfer reactions.
2.1 Objectives
 Understand the concept behind the kinetics and mechanisms of
reactions in solution.
 Explain the different types of ligand displacement reactions in
octahedral complexes.
 Understand the mechanisms behind substitution reactions in square
planar complexes and the importance of Tran‘s effect.
 Learn about the electron transfer reactions.
13
2.2 Kinetics and Mechanisms of Reactions in Solution
Complementary Reactions Thermodynamics: When examining thermodynamics of a reaction we are
entirely interested in the start and finish of a reaction. What is the extent
of reaction? Where does theequilibrium lie? How do we investigate this?
Kinetics: How fast does a reaction reach equilibrium? This relates
directly to the mechanism.
NOTES Substitution reactions involve either replacement of ligands by
other ligands- nucleophilic substitution (SN) or replacement of central
metal ion by other metal ions- electrophilic substitution (SE) which is
rare.
Two main types of nucleophilic substitution mechanisms are,
1) Unimolecular nucleophilic substitution (SN1) or Dissociative
mechanism
2) Bimolecular nucleophilic substitution (SN2) or Associative or
Displacement mechanism
Unimolecular Nucleophilic Substitution (SN1) or Dissociative
mechanism
According to this mechanism, the complex first undergoes
dissociation losing the ligand to be replaced, X and changes into a five
coordinated intermediate which then readily adds the new ligand, Y.
[MX6] → [MX5] + X -slow step
[MX5] + Y → [MX5Y] -fast step
The characteristics of this reaction are,

1. Only one species, [MX6] is involved in the formation of the
activated species in the slow step.
2. In the second step, the activated species undergoes fast
reaction with incoming ligand, Y.
3. The activation energy for the first step is high and that for the
second step is low.
4. The rate of the overall reaction depends on [MX6] and not on
[Y].
5. The reaction is first order with respect to MX6and is zero
order with respect to Y.
6. In the formation of the activated complex, the coordination
number of the metal ion is decreased by one.
7. The rate law for the substitution is ν = k1[MX6]
Example for a reaction undergoing this mechanism is,
[Cr(H2O)6]3+ → [Cr(H2O)5]3+ + H2O (slow)
[Cr(H2O)5]3+ + CN-→ [Cr(H2O)5CN]2+
Types of intermediates formed during SN1 reaction
Consider an octahedral complex MA5X being attacked by a
nucleophile, Y. If the reaction proceeds through a dissociative S N1
mechanism, two types of intermediates can be formed.
1) The bond M-X dissociates causing least disturbance to the
remaining MA5 intermediate which has a square pyramidal
14
geometry. The intermediate MA5 is then attacked by Y to
produce MA5Y.
2) The bond M-X dissociates and the remaining MA5species ComplentaryRreactions
immediately adjust the bond angles to produce a trigonal
bipyramidal intermediate which is then attacked by Y to
produce MA5Y.
It is evident that the formation of a trigonal bipyramidal
NOTES
intermediate involves the movement of atleast two metal ligand bonds

whereas no such movement is required during the formation of a square
pyramidal intermediate. SN1 reactions thus proceed generally through the
more stable square pyramidal intermediate unless the trigonal
bipyramidal intermediate is stabilized by pi bonding.
Bimolecular Nucleophilic Substitution (SN2) or Associative or
Displacement mechanism
According to this mechanism, the new ligand first adds on to the
complex to form a seven coordinated activated or intermediate complex
which then readily undergoes dissociation to yield the final product.
[MX6] + Y → [MX6Y] -slow step
[MX6Y] → [MX5Y] + X -fast step
In this case, the reaction rate depends upon the first step. i.e upon the
concentrationof the complex as well as the concentration of the incoming
ligand Y.
The characteristics of this reaction are,
1. In this reaction, two species (MX6 and Y) are involved in the
formation of the activated species; Y is added to the reactant
complex to form the activated species.
2. In the second fast step, the activated complex loses a ligand and
the new ligand Y becomes a permanent part of the molecule.
3. The rate of the overall reaction depends on both [MX6] and [Y].
15
4. The reaction is first order with respect to MX6and first order with
Complementary Reactions respect to Y; the overall order is 2.
5. In the formation of the activated species, the coordination number
of the metal is increased.
6. The general rate law for the substitution is ν = k 1[MX6] [Y].
Example for a reaction undergoing this mechanism is,
NOTES [Co(NH3)5Cl]2+ + H2O → [Co(NH3)5Cl H2O]2+ → [Co(NH3)5H2O]3+ + Cl-
Types of intermediates formed during SN2 reaction
If the reaction proceeds through an associative S N2 mechanism,
there are two types of intermediates.
If the nucleophile Y attacks through one of the edges of the octahedron, a
pentagonal bipyramidal intermediate is formed. The formation of
pentagonal bipyramidal intermediate requires the movement of atleast
four ligands to adjust the nucleophile Y. The ligand- ligand repulsions
also increase the energy of pentagonal bipyramidal intermediate because
the decrease in A-M-A bond angles brings the electron pairs of metal
bonds nearer to one another in this intermediate.
The second type of intermediate is formed if the nucleophile Y

attacks through the middle of one of the triangular faces of the
octahedron. As soon as Y starts approaching M, the outgoing ligand X
starts moving towards the middle of another triangular face so that the
octahedral wedge intermediate formed has both X and Y ligands in
equivalent positions. The formation of an octahedral wedge intermediate
requires minimum movement of ligands and the ligand- ligand repulsions
are less than the repulsions in pentagonal bipyramidal intermediate. i.e it
requires less energy than pentagonal bipyramidal intermediate. Therefore
SN2 reactions generally proceed through an octahedral wedge
intermediate.
16
SN1 Vs SN2 mechanisms
SN1 and SN2 mechanisms can be differentiated from each other by
the following points. ComplentaryRreactions
1) In SN1 process, the rate determining slow step is a metal ligand
bond breaking step, and the coordination number of the complex
is reduced from 6 to 5. In SN2 process, the rate determining step
involves a metal ligand bond making step and the coordination
NOTES
number is increased to 7.
2) The rate of SN1 mechanism is first order with respect to MX6. i.e
rate determining is unimolecular. On the other hand, the rate
determining step for SN2mechanism is bimolecular. i.e its
reaction rate is second order: first order with respect to MX 6 and
first order with respect to Y.
SOLVOLYTIC REACTIONS
Consider a substitution reaction of octahedral complex[MX6]n+ in
presence of a ligand Y- in aqueous medium. Since water also acts as a
ligand and is much more abundant than Y -, aquation occurs called as
solvolytic reaction.
[MX5Y]n+ + H2O→ [MX5(H2O)](n+1)++ Y-
The reaction in aqueous medium in which a water molecule
replaces a coordinated ligand from the complex species is termed as
aquation reaction or acid hydrolysis. The reaction in aqueous medium in
which the anion of water molecule i.e OH - ion replaces a coordinated
ligand from the complex species is termed as base hydrolysis.
[MX5Y]n+ + OH-→ [MX5(OH)]n++ Y-
Since some OH- ions are always present due to auto ionization of
H2O, some [MX5(OH)]n+is always formed along with
(n+1)+
[MX5(H2O)] during the hydrolysis of [MX5Y]n+even in neutral
aqueous medium.
2.2.1 Labile & Inert Complex

Many reactions require substitution, replacing one ligand by
another.In the kinetic sense, it is more proper to call the complexes inert
or labile rather than stable or unstable ones. The term labile is applied to
very reactive complexes whereas less reactive complexes are called inert.
Taube has defined labile as systems which undergo substitution reactions
within 1 minute at room temperature and in 0.1 solutions. Labile
Complexes are those undergoing substitution with t ½< 1 minute. For
eg.Cu(NH3)4(H2O)22+ is a labile or fast reacting complex. When a
solution containing this blue species is added to concentrated
hydrochloric acid, the solution turns green rapidly as the solutions are
mixed
Cu(NH3)4(H2O)22+ + 4H+ + 4Cl- CuCl42- + 4NH4+ + 2H2O
17
The term inert is used for reactions that are either too slow to
Complementary Reactions measure or slow enough to follow at ordinary conditions by conventional
techniques. Eg : The complex Co(NH3)63+ is an example of a relatively
inert or slow – reacting complex. The complex must be heated in 6M
hydrochloric acid for many hours to obtain any perceptible amount of the
chloro complex.
NOTES Co (NH3)63+ + H+ + Cl- Co (NH3)5 Cl2+ + NH4+
Inert complexes undergoing substitution with t ½> 1 minute. Inert doesn‘t

mean unreactive and Inert doesn‘t mean thermodynamically stable. Inert
does mean slow to react (also known as Robust). For example
[Fe(H2O)5F]2+ = labile, but it is very thermodynamically stable

[Co(NH3)6]3+ = inert, but thermodynamically unstable.
Inert complexes react slowly, so their products can be isolated and
studied. Those with large LFSE, d3, low spin d4-d6 are inert metal ions.

1. The size of the central atom affects the case with which ligands can be
replaced. The smaller the central atom, more tightly the ligands are held
and the more inert the complex is formed.
2. The higher the charge of the central ion, more inert the complex is.
3. The degree of lability or inertness of a transition – metal complex can
be correlated with the d-electron configuration of the metal ion. If a
complex contains electron in the antibonding eg* orbitals, the ligands are
expected to be relatively weakly bound and are to be easily displaced. If
a complex contains an empty t 2g orbital, the four lobes of that orbital
correspond to directions from which an incoming ligand can approach
the complex with little electrostatic repulsion. Therefore one concludes
that a complex of a central ion with one or more e g* electrons or with
fewer 3d electrons should be labile and that a complex with any other
electronic configuration should be relatively inert.
A well-studied class of substitution reactions involves aqueous metal ions
([M(H2O)m]n+) as reactants. These reactions can produce coloured
products used to identify metal ions:
[Ni(H2O)6]2+ + 6 NH3 [Ni(NH3)6]2+ + 6H2O

Green blue
Fe(H2O)6]3+ + SCN- [Fe(H2O)5(SCN)]2+ + H2O

Very pale violet Red
18
ComplentaryRreactions
[Fe(H2O)5(OH)]2+ + H+ [Fe(H2O)6]3+
Yellow Colourless (very pale violet)
[Fe(H2O)6]3+ + Cl- [Fe(H2O)5(Cl)]2+ + H2O NOTES

Yellow
[Fe(H2O)5(Cl)]2+ + PO43- Fe(H2O)5(PO4) + Cl-

Colourless
Fe(H2O)5(PO4)+ SCN- [Fe(H2O)5(SCN)]2+ + PO43-

Red
[Fe(H2O)5(SCN)]2+ + F- [Fe(H2O)5(F)]2+ + SCN-

Colourless
Ligand substitution reactions involving [M(H2O)m]n+ are rapid and

generally form species that also undergo fast reactions. Addition of
HNO3, NaCl, H3PO4, KSCN, and NaF successively to a solution of
Fe(NO3)3.9H2O provides a classic example. The initial solution is yellow
because of the presence of [Fe(H2O)5(OH)]2+and other Fe(III) complexes
containing water and hydroxide ligands derived from the hydrolysis of
[Fe(H2O)6]3+. Although the exact complexes formed and their
equilibrium concentrations depend on the concentrations of the ions
involved, these products are representative:
While the fate of these reactions is partially governed by the relative
bond strengths between Fe(III) and the incoming and departing ligands,
the examination of water exchange reactions,is insightful since the bonds
broken and made during the substitution have essentially identical
strengths. Water exchange rate constants vary widely as a function of the
metal ion.
Rate constants like those in are known for many substitution reactions,
and general trends in the speeds of these reactions have been correlated
to the electronic configuration of the starting complex. The rate constants
for water exchange differ by more than 13 orders of magnitude for
[Cr(H2O)6]3+ and [Cr(H2O)6]2+ .It is also intriguing that [V(H2O)6]3+
undergoes water exchange roughly 6 times faster than does [V(H2O)6]2+,
[M(H2O)m]n+ + H218O [M(H2O)m-1(H218O)]n+ + H2O
19
Complementary Reactions
Complex colour electron water exchange
config. rate (s−1, 25 °C)
[Ti(H2O)6]3+ violet (t2g)1 1.8 x 105
NOTES [V(H2O)6]2+ violet (t2g)3 8.7 x 101
[V(H2O)6]3+ yellow (t2g)2 5.0 x 102
[Cr(H2O)6]2+ blue (t2g)3(eg)1 1.2 x 108
[Cr(H2O)6]3+ violet (t2g)3 2.4 x 10−6
[Mn(H2O)6]2+ pale pink (t2g)3(eg)2 2.1 x 107
[Fe(H2O)6]2+ blue-green (t2g)4(eg)2 4.4 x 106
[Fe(H2O)6]3+ pale violet (t2g)3(eg)2 1.6 x 102
[Co(H2O)6]2+ pink (t2g)5(eg)2 3.2 x 106
[Ni(H2O)6]2+ green (t2g)6(eg)2 3.2 x 104
[Cu(H2O)6]2+ blue (t2g)6(eg)3 4.4 x 109
[Zn(H2O)6]2+ (t2g)6(eg)4 >107
Rate Constants for Water Exchange in [M(H2O)6]n+
The reactions of Coordination Complexes may be divided into three
classes:
i) Substitution at the metal center
ii) Reactions of the coordinated ligands
iii) Oxidation and Reduction reactions at the metal center.
For the purposes of our discussion we will confine our discussion to (i)
for substitution reactions on Octahedral and Square Planar
complexes.We will only briefly discuss one specific reaction involving
acoordinated ligand.
2.3 Ligand Displacement Reactions in Octahedral Complexes
2.3.1 Hydrolysis in Octahedral Complexes:
These are the substitution reactions in which a ligand isreplaced by a
water molecule or by OH - groups. The reactions in which an aqua
complex is formed by thereplacement of a ligand by H 2O molecule are
called acidhydrolysis or aquation.The reactions in which a hydroxo
complex is formed by thereplacement of a ligand by OH - group are called
basehydrolysis.
Substitution in octahedral complexes
Intimate and stoichiometric mechanisms
Let us consider the following reaction:
L5MX + Y L5MY + X,
20
where X is the leaving group and Y is the entering
These reactions can be explained in two ways: (1) intimate mechanism
and (ii) stoichiometric mechanism ComplentaryRreactions
Dissociative and associative activations are known as intimate
mechanism. In dissociative activation, breaking of the bond between the
metal and the leaving group is important and in associative activation,
bond formation between the metal and the entering ligand is important.
NOTES
The sequence of elementary steps from reactants to products is called
stoichiometric mechanism.
Dissociative Reaction mechanism
 formation of an intermediate
 coordination number of the intermediate is lower than that in the
starting complex
 corresponds to SN1 mechanism for organic compounds
Associative Reaction Mechanism
 two-step pathway
 formation of an intermediate
 coordination number of the intermediate is higher thanthat in the
starting complex.
Interchange Reaction Mechanism
 Bond formation between the metal and entering group is
concurrent with bond cleavage between the metal and the leaving
group.
 corresponds to SN2 reaction in organic chemistry
 no intermediate
Dissociative and associative mechanismsinvolve two-step pathways and
anintermediate.An interchange mechanism is a concertedprocess where
there is no intermediate.
Intimate mechanism
2.3.2 Anation in Octahedral Complexes
These are the reactions in which an aquo ligand (H2O molecule) from an
aquo complex is replaced from the co-ordination shell by some anion. It
appears that the ligand displacement reaction like,
Ka
n+ - (n-1)+
[M(OH2)6] + X [M(OH2)5X] + H2 O
This type of reaction is important as its behavior indicates not only how
new complexes are formed but also where coordinated water is replaced
by X-.
n+ - (n-1)+
[L5M(OH2)] +X [L5MX] + H2O
Generally two observations can be drawn:
21
 For a given aqua ion, the rate of anation show little
Complementary Reactions dependence on the nature of ―L‖.
 The rate constant for anation of a given aqua complex is
almost the same as for H2O exchange.
An anation reaction is the reverse of acid hydrolysis reaction (aquation).
Kinetic studies of these reactions in aqueous solution show that these are
NOTES bimolecular reactions with rate depends on the concentrations of the
complex and Y.It always goes via the aquo complex, i.e. in two steps, the
replacement of one ligand with water, then water is replaced with another
ligand.
The following reaction proceeds through an intermediate Co(CN) 52-
[Co(CN)5H2O]2-[Co(CN)5]2- + H2O
[Co(CN)5]2-+ X-[Co(CN)5 X]3-
2.3.3 Aquation In Octahedral Complexes (AcidHydrolysis)

The replacement of ligand X by H2O is called aquation, where X is the
labile ligand.
[ML5X]n+ + H2O [ML5H2O](n+1)+ + X
Occurs in neutral and acid solutions (pH<3).Rate is independent of water
molecule
[Co(NH3)5x]2+ + H2O  [Co(NH3)5(H2O)]3+ + x-
The rate of such reactions are pH dependent and generally follow the rate
law
 = KA[L5CoX] + KB[L5CoX] [OH-]
In general, KB (for base hydrolysis) is some 104 times KA (for
acid hydrolysis)
Thus the rate law does not tell us whether H2O is involved in the rate –
determining step.
MECHANISMS OF ACID HYDROLYSIS
Dissociative Mechanism
Associative Mechanism
Factors affecting these reactions

Nature of the entering or leaving group
22
Let us consider the complex, [Co(NH3)5X]n+. The rates of aquation for
this complex very much depends on the nature of the leaving group, X.
2+ Complementary and Non-
As an example, for the complex, [Co(NH3)5(NO3)] , k is of the order of ComplentaryRreactions
-5 -1
10 s . When I - is present instead of NO3-, the rate decreases and is of
-6 -1
the order of 10 s for the complex, [Co(NH3)5I]2+. Both NO3- and I - are
leaving groups. The reaction slows down when the leaving group is I -. In NOTES
the case of the complex, [Co(NH3)5F], the rate is the order of 10 -8. That
is, the reaction further slows down. Thus it is proved that M-X bond
breaking is very much important in aquation reactions than bond
formation.
Anation reactions do not depend very much on the nature of the
entering group, Y-. Instead, it is very much dependent on the nature of
the bond being broken. Experimental datashow that the rate is of the
-6
order 10 for the different entering groups (Y-), N3-, SO42- , Cl- or NCS-
clearly indicating that the rate is independent of the nature of the
entering group.
Steric effects of inert (non-leaving) ligands

When the non-leaving ligands are bulky, they will be crowding the
central metal ion and hence, the incoming ligand will find it difficult to
approach the central metal ion slowing down the rate of reaction taking
place by associative mechanism. Instead, if the reaction takes place by
dissociative mechanism, (that is, one ligand breaks first and then a new
ligand approaches), the rate of the reaction will increase because the
crowding around the metal ion is reduced.
Electronic effects of inert ligands
If the existing ligand is capable of π-donation to the metal and stabilize
the transition state, the reaction will be fast. When a reaction takes place
by dissociative mechanism, when a ligand leaves, the metal becomes
electron deficient. If there is a cis-ligand and if it is capable of donating
electrons by forming π-bond with the electron deficient metal, then it
stabilizes the transition state by lowering the energy and hence the
reaction takes place faster.
Effect of charge
The increase in positive charge decreases the rate of reaction following a
dissociative mechanism because the breaking the metal-ligand bond
becomes difficult.
2.4 Substitution Reactions In Square Planar Complexes.
Square planar complexes with d8 configurations undergo substitution

reactions of the type,
23
Complementary Reactions
NOTES
in which Y is the entering nucleophilic ligand, X is the leaving
ligand and T is the ligand trans to X.
Mechanism
Pt(II) complexes are widely used for studying the mechanism and
kinetics since the substitutions are comparatively slow and hence easier
to study. From kinetic studies scientists have arrived at an associative
SN2 mechanism for substitution reactions in square planar complexes.
Consider a nucleophile Y attacking a d8 complex from either side of the
plane. In addition to being attracted to the electron deficient metal centre,
the ligand experiences repulsion from the filled metal d orbitals and from
the bonding electrons. However, it coordinates to the metal through an
empty pz orbital to form a square pyramidal species, though electronic
repulsions as well as steric factors slow the attack. Once formed, the
square pyramidal species will undergo a transformation to a trigonal
bipyramidal structure. It will have three ligands (Y, T and X) in its
equatorial plane and two of the groups that were trans to each other in the
original complex will occupy the axial positions. As X departs from the
trigonal plane, the T-M-Y angle opens up and the geometry will pass
through a square pyramid on its way to the square planar product.
The trigonal bipyramidal species that forms during the reaction

may exist either as an activated complex or as a true intermediate. The
distinction between the two depends on the lifetime of the species. The
term activated complex refers to the configuration of the reactants and
products at a peak in the reaction profile energy curve. i.e at the transition
state. The term intermediate implies that a species has a detectable
24
lifetime (though short) and that it is at least somewhat more stable than
any activated complexes.
NOTES
Reaction coordinate/energy profile for a square planar substitution

reaction having a) trigonal bipyramidal activated complex and b) a
trigonal bipyramidal intermediate.
Evidences for the mechanism
The mechanism of substitution reactions of square planar complexes
appears to be associative SN2 rather than dissociative SN1. The evidences
for this are,
1. In the case of square planar complexes of Ni(II), Pd(II) and Pt(II),
five empty orbitals of comparable energy can be made available
for bonding of which four are used up for bonding with ligands.
The fifth orbital can easily accommodate electrons from the
attacking ligand forming a five coordinate intermediate. i.e an
associative SN2 mechanism.
2. There exists a parallelism between the reactivity of the square

planar complexes of Ni(II), Pd(II) and Pt(II) complexes (Ni(II) >
Pd(II) > Pt(II)) and their ease with which these expand their
coordination no: which indicates the formation of an intermediate
with a higher coordination no:.
3. The rates of aquation reactions of [PtCl4]2-, [PtCl3NH3]-, cis
[Pt(NH3)2Cl2] and [Pt(NH3)3Cl]+ changes only by a factor of 2
whereas the charge of the complex changes from -2 to +1. This
suggests that both bond breaking and bond making are important,
which is characteristic of an associative SN2 mechanism.
4. Nature of the entering ligand greatly affects the rate of

substitution in square planar complexes indicating that the
entering ligand takes part in the rate determining step. This is
another evidence for SN2 mechanism.
25
Complementary Reactions 5. The nature of the departing group, does not affect much the rate
constants of these reactions indicating that the dissociative S N1
mechanism in which the departing ligand has a greater role is not
operative.
NOTES 6. It has been observed that substitution in Pt(II) square planar

complexes occurs with retention of configuration. i.e cis → cis
and trans → trans. This is in agreement with a trigonal
bipyramidal intermediate. With a 3 coordinate intermediate
(dissociative mechanism), the entering group can lead to both cis
and trans isomers.
7. As the bulkiness of the ligands other than the entering and

departing ligands increases, the reaction rate decreases, indicating
an associative mechanism.
Kinetics
The kinetics of the reaction can be illustrated by the reaction,
[PtA3X]n+ + Y- →[PtA3Y]n+ + X- in the presence of water.
For this reaction, a two term rate law was found out.
Rate = k1[PtA3X]n+ + k2[PtA3X]n+[Y-]
where k1= first order rate constant for solvent controlled reaction and k 2=
second order rate constant for reaction with Y -. The analysis of the rate
constants is made by conducting the reactions with a large excess of
nucleophile,Y-. Then the observed rate constant, kobs is pseudo first order
and is related to k1 and k2 as kobs = k1+ k2[Y-]. Thus for the same
complex, linear plots of kobs against different nucleophile
concentration,[Y-] should be obtained, having the same interceptsk 1 and
different slopes, k2.
26
Plots of kobs for the reaction: [Pt(dien)Cl]+ + Y- → [Pt(dien)Y]+ + Cl- against
concentration of nucleophile, [Y-]
The obtained rate law indicates that the reaction of ComplentaryRreactions
[PtA3X]n+withY-to yield [PtA3Y]n+is occurring by a two path mechanism,

of which only one involves Y -in the rate determining step.
NOTES
The upper path is the solvent path (also called Y-independent

path) and the lower path is the direct path (reagent path). In the solvent
path, the solvent H2O replaces X- in a slow step. It is subsequently
replaced by Y-in a rapid step. Experiments show that Y-independent path
is not an SN1 process, but is a direct SN2 displacement of leaving group
by nucleophile in probably second order path while the solvent path gives
pseudo first order kinetics.
The rate constant k1 is due to solvent path, while k2 is due to the
direct displacement of the leaving group by nucleophile. Hence solvent
path k1 can be designated as ks and the direct displacement path k2 as kY
so that
kobs = ks+ kY[Y-]
Factors affecting the rates of substitution reactions in square planar
complexes
1. Trans Effect(discussed later)
2. Effect of leaving group
For the reaction, [Pt(dien)X]+ + py →[Pt(dien)py]2+ + X-, the
rates of the reaction show that if the leaving group X -is replaced by NO3 -,
H2O, Cl-, Br-, I-, N3-, SCN-, NO2- and CN-, the rates decrease in the order,
NO3-> H2O > Cl-> Br-> I-> N3-> SCN-> NO2 -> CN-
3. Solvent Effect
27
Since in the solvent path, the solvent replaces directly, as
Complementary Reactions the coordinating ability of the solvent increases, contribution
made by this path to the overall rate of the reaction would also
increase.
4. Effect of charge on the complex

NOTES The charge on the complex does not have appreciable effect on
the rate of nucleophilic substitution of square planar complexes. For
example, the rates of aquation reactions of [PtCl4]2-, [PtCl3NH3]-, cis
[Pt(NH3)2Cl2] and [Pt(NH3)3Cl]+ changes only by a factor of 2 whereas
the charge of the complex changes from -2 to +1.
In general there are two factors contributing to trans direction of
substitution as described below:
1) Trans influence: This is a thermodynamic factor. Some ligands
weaken the M-L bond trans to them in the ground state and thus by
facilitating the substitution.
E.g. Strong σ- donors like H-, I-, Me-, PR3 etc., destabilize the M-L bond
trans to themselves and thus by bringing the easy substitution of that
ligand.
2) Trans effect: This is a kinetic factor and considered as true trans
effect. It occurs by the stabilization of the transition state.
E.g. The strong π-acceptors like NO+, C2H4, CO, CN- etc., stabilize the
transition state by accepting electron density that the incoming
nucleophilic ligand donates to the metal through π-interaction.
Note: This is debatable since the π-interaction may increase the strength
of M-L bond especially in the trans position.
2.4.1 Trans Effect

The ability of an attached group to direct substitution into a
position trans to itself is called trans effect. Such a group has a marked
influence (trans influence) on the rate of a reaction. For example, in the
substitution reaction,
Since Cl- has greater trans effect than NH3, the Cl- trans to Cl- and not the
one trans to NH3 is replaced by C2H4. Also,
28
NOTES
- -
Since C2H4 has greater trans effect than Cl , the Cl trans to C2H4 and not
the one which is trans to Cl- is replaced by NH3. The approximate
ordering of ligands in a trans directing series is,
CN-, CO, NO, C2H4> PR3, H-> CH3-, C6H5-, SC(NH2)2, SR2> SO3H->
NO2-, I-, SCN-> Br-> Cl-> py > RNH2, NH3> OH- > H2O
Trans effect is used in synthesizing certain specific complexes.
For example cis and trans diamminedichloro Pt(II) complexes have been
synthesized separately as,
Another application of trans effect is in distinguishing cis and

trans isomers of the formula [PtCl2(NH3)2]. Addition of thiourea (tu) to
the trans isomer results in the replacement of the two trans Cl- ions. The
reaction stops at this stage because the trans NH3 molecules do not
labilise each other.
29
But the addition of thiourea to the cis isomer results in the
Complementary Reactions displacement of all the original ligands and gives [Pt(tu)4]2+ as the final
product.
NOTES
The trans effect of the ligands decreases in the order tu> Cl- > NH3. This
method of differentiating the geometrical isomers is called the Kurnakov
effect.
Theories of trans effect
Several theories have been proposed for the explanation of trans effect.
1) Polarisation theory
This is a thermodynamic approach. According to this theory, the
primary positive charge of Mn+ induces a dipole in all the four ligands. If
all the four ligands are identical as in (a), then the dipoles induced by the
metal ions cancel each other and the resultant dipole is zero. None of the
four ligands show trans effect. But if the four ligands are not identical,
then the induced dipoles do not cancel each other. The two L ligands
which are similar and trans to each other balance each other. But the
other two trans ligands T and D, which are not similar do not balance
each other. T is large and has greater polarisability than D. Polarisation
takes place in such a way that the positive charge of M n+ central ion at a
point trans to T is reduced. Hence the attraction of D for M n+ is also
reduced and the bond trans to T is weakened and hence lengthened. This
facilitates the replacement of D by E (entering ligand) at a point trans to
T.
30
Evidences: 1) The theory predicts that trans effect is important only when
the central metal ion itself is polarisable and large in size. Actually, trans ComplentaryRreactions
effect is observed predominantly in Pt(II) complexes than in Pd(II) or
Ni(II) complexes. 2) If the ligand T is highly polarisable in [PtL2TD]
complex, then Pt-D bond trans to T is longer than Pt-L bond cis to T. The
complex [Pt(C2H4)X3]- type where X= Cl-, Br- and C2H4 has large trans NOTES
effect. The Pt-Cl or Pt-Br bond trans to C2H4 is longer than that cis to
C2H4.
Limitations: The theory can well explain the ligands at the low end of the
trans effect series like H2O, OH-, NH3 etc. However, this theory cannot
explain the high trans effect of the pi bonding ligands like C2H4, CN-, CO
etc which lie at the other end of trans effect series.
2) Pi bonding theory
According to this theory, the vacant π or π* orbitals of the pi
bonding ligands accept a pair of electrons from the filled d orbitals of
the metal (dxz or dyz) to form M-L pi bond. In the case of Pt(II) square
planar complex, [PtL2TD] (T is the pi bonding ligand, D is the departing
ligand trans to T), the filled orbital of Pt(II) overlaps with the empty
orbital of the ligand T to form M-T pi bond. The formation of this pi
bond increases the electron density in the direction of T and diminishes
it in the direction of the ligand trans to T. The electron shift towards T
facilitates the approach of the entering ligand E with its lone pair in the
direction of trans directors.
The formation of dπ – pπ bond between Pt(II) and the π- bonding ligand,

T in the five coordinated transition complex.
3) Molecular Orbital approach
31
In this approach, there is the formation of a five coordinated
Complementary Reactions intermediate with trigonal bipyramidal arrangement in which the more
electronegative atoms occupy the axial positions. The loss of the ligand L
from the triangular plane will take place from trans position to the least
electronegative group T so that the entering group E is trans to T.
NOTES Cis Effect

Certain ligands such as thiocyanate and hydroxide ions greatly
accelerate the hydrolysis of a complex when they are cis to the leaving
group as compared to the analogous reaction in which the leaving group
is trans to these ligands. For example,
[Co(en)2XCl]n+ + H2O → [Co(en)2X(H2O)]n+ + Cl-
where X is a cis activating ligand like OH -, SCN- etc. When OH- is cis to
the leaving Cl-, the reaction rate is about ten times as great as that when it
is in the trans position. The ligands that possess a strong cis effect are
those that have unshared pairs of electrons in addition to the pair used in
the sigma dative bond.
2.5 Electron Transfer Reactions Or Redox Reactions

Transition metals can undergo several oxidation- reduction
reactions where in there is a change in oxidation state. There are formally
two types of reactions of this type.
 Reactions involving simple electron transfer
[Fe(CN)6]4- + [Ir(Cl)6]2- →[Fe(CN)6]3- + [Ir(Cl)6]3-
 Reactions that can be considered as atom transfer reactions that
occur with electron transfer
[Co(NH3)5Cl]2+ + [Cr(H2O)6]2+ → [Co(H2O)6]2+ + [Cr(H2O)5Cl]2+
Simple electron transfer reactions involving transition metal
complexes in solutions are complicated by the fact that the oxidised and
the reduced species are often metal ions surrounded by shields of ligands
and solvating molecules. No heat change is associated with the reaction.
The reactions can be between two metal ions or between single element
in different oxidation states (self exchange reactions). The electron
transfer can be broadly divided into two mechanistic classes called outer
sphere mechanism and inner sphere mechanism.
1. What is meant by inert and labile complexes?

2. Give any two factors affecting inert and labile complexes?
3. Give some ligand displacement reactions in octahedral complexes.
4. Define the termTrans effect

32
1.Transition metal complexes which undergo rapid substitution of one
ligand for another are labile, whereas complexes in which substitution
proceed slowly or not at all are inert. Labile means a relatively stable but ComplentaryRreactions
reactive species whereas inert means unreactive. A compound in which
metal-ligand bonds are easily broken is referred to as "labile." A labile
complex has a very low activation energy for ligand substitution whereas
an inert complex has a very high activation energy.
NOTES
2. The factors affecting inert and labile complexes are
 Size of the central metal ion.

 Charge on the central metal ion.
3. The ligand displacement reactions in octahedral complexes are
 Aquation reaction (Acid hydrolysis)
 Anation reaction
4. The Trans effect can be defined as the effect of a ligand over rate of
substitution of another ligand positioned Trans to it in the square planar
complexes.
2.8 Summary
 The rate at which one complex converts into another is governed
by the height of the activation energy barrier that lies between
them. Thermodynamically unstable complexes that survive for
long periods (by convention, at least a minute) are commonly
called ‗inert‘ (non-labile) and the complexes that undergo more
rapid equilibration (less than a minute) are called ‗labile‘.
 The reactions in which an aqua complex is formed by
thereplacement of a ligand by H2O molecule are called
acidhydrolysis or aquation.
 The reactions in which a hydroxo complex is formed by the
replacement of a ligand by OH - group are called base hydrolysis.
 An anation reaction is the reverse of acid hydrolysis reaction
(aquation) in which the water molecule is replaced by any ligand.
 The spectator ligands T that are trans to the leaving group in
square-planar complexes influence the rate of substitution. This
phenomenon is called the trans effect.A strong σ-donor ligand or
π-acceptor ligand greatly accelerates substitution of a ligand that
lies in the trans position.
2.9 Keywords
33
Inert complex - Thermodynamically unstable complexes that survive for
Complementary Reactions long periods
Labile complex - Thermodynamically stable complexes that survive for a
very short period of time i.e., the half-life of the complex is less than a
minute.
Trans effect - The Trans effect can be defined as the effect of a ligand
NOTES over rate of substitution of another ligand positioned trans to it in the
square planar complexes.
1. Explain in detail about labile and inert complexes with example.
2. Give a brief review about ligand displacement reactions in octahedral
complexes.
3. Give a brief overview about the ligand substitution reactions in square
planar complexes.
4. Explain the trans effect.
5. What is meant by electron transfer reactions?
1. Huheey, J.E., E.A. Keiter and R.L. Keiter. 2002. Inorganic
Chemistry: Principles of Structure and Reactivity, 4th Edition.
New York: HarperCollins Publishers.
2. Gary L. Miessler., Paul J. Fischer., Donald A. Tarr. Inorganic
Chemistry, 5th ed : Pearson
3. Shriver and Atkins., Inorganic Chemistry, 5th ed : W. H. Freeman
and Company New York.
4. Ajai Kumar., Coordination chemistry, 2nded :Aaryush educations.
34
UNIT- 3 COMPLEMENTARY AND NON-
COMPLEMENTARY REACTIONS Complentary Reactions
Structure
3.0 Introduction
3.1 Objectives
3.2 Complementary and Non- Complementary reactions NOTES
3.3 The classification of redox reactions
3.4 Outer-sphere mechanism
3.5 Inner-sphere mechanism
3.6 Isomerization and racemization
3.7 Template effect and synthesis of macrocyclic ligands
3.10 Summary
3.11 Keywords
3.0 Introduction
Redox reactions in which the oxidant and reductant change their
oxidation states by an equal number of units are called complementary
reactions. Non- complementary reactions proceed through multistep,
each step involving a single electron transfer in which the intermediates
of unstable oxidation states are formed. Oxidation–reduction reactions of
transition-metal complexes involve electron transfer from one complex to
another. The two molecules may be connected by a common ligand
through which the electron is transferred (inner-sphere reaction), or the
exchange may occur between two separate coordination spheres (outer-
sphere reaction). Electron transfer rates depend on the rate of ligand
substitution within the reactants, the match of the reactant orbital
energies, solvation of reactants, and the nature of the ligands.
3.1 Objectives
 Explain about the electron transfer mechanisms or classification
of redox reactions.
 Understand about the inner sphere and outer sphere mechanisms.
 Understand the concept of racemization and isomerization in a
precise manner.
 Explain about the template effect.
 Learn about the synthesis of macrocyclic ligands
35
3.2 Complementary and Non-Complementary Reactions
Complementary Reactions Complementary reactions are reactions in which number of
electrons gained by one species is equal to number of electrons lost by
the other.
There are some elements that have stable oxidation states
differing by two electrons, without a stable state in between. It has been
NOTES shown that in the majority of these cases, if not in all, two – electron
transfer occurs. Two electron transfers have been suggested for the
oxidation of Hg22+ by Tl3+ and for the Tl3+ - Tl+ exchange reaction. In the
latter case, the formation of Tl2+ is also possible, but the rate law for the
former reaction.
K [Hg2+] [Tl3+]
[Hg2+]
Hg22+ Hg2+ + Hgo
Hgo + Tl3+ Hg2+ + Tl+
The exchange reaction of Tl+ - Tl3+ which has been extensively studied is
considered. Nevertheless, there is still not agreement as to whether the
reaction occurs in a single two – electron transfer step or in a series of
steps with unstable Tl2+ as an intermediate. The extreme sensitivity
which Tl2+ shows that the exchange goes by this intermediate. The
hydrolysis reaction,
Tl(H2O)n3+ Tl(H2O)n-1 OH2+ + H+
introduces a pH dependence for the rate.

The mechanism would be
Tl3+ + Tl+ Tl+ + Tl3+
TlOH2+ + Tl+ Tl+ + TlOH2+
or
Tl3+ + Tl+ 2Tl2+
TlOH2+ + Tl+ TlOH+ + Tl2+
Tl2+ + Tl3+ Tl3+ + Tl2+
Tl2+ + Tl+ Tl+ + Tl2+ etc,
In the presence of other anions more complicated rate laws are found,
indicating that two – electron transfers occurs through various Tl3+
complexes.
A number of other redox reactions also appear to proceed by two electron
transfers, examples are,
36
SnII + TlIII  SnIII + TlI
SnII + HgII  SnIV + Hg0
Unit -4 Spectral
VII + TlIII  VIII + TlI properties of
complexes
All these reactions are complementary meaning that in the overall
stoichiometry the oxidant gains and the reductant loses two electrons.
Non – Complementary Reactions
Reactions of a non – complementary type, ie the number of NOTES
electrons gained by one ion of one species is not equal to the number, lost
by the other, must have multistep mechanisms, since ternary activated
complexes are not likely and are not supported by an experimental
evidence. This, is in turn, means that some relatively unstable
intermediate must be generated. For eg, the overall reaction of Fe2+ with
Tl3+ (eqn1) might have as its initial step either a one – electron transfer to
generate Fe3+ and the unstable Tl2+ or a two – electron transfer to
generate Tl+ and the unstable Fe4+. It has been reported that the addition
of Fe3+ reduces the rate of reaction, but the addition of Tl+ is without
effect. This indicate that the mechanism would be that of eqn2 and 3.
Tl3+ (aq) + 2Fe2+ (aq)  Tl+(aq) + 2Fe3+ (aq) ------------------- 1

Fe2+ (aq) + Tl3+ (aq)  Fe3+ (aq) + Tl2+ (aq) --------------------- 2
Fe2+(aq) + Tl2+ (aq)  Fe3+ (aq) + Tl+ (aq) ----------------------- 3
3.3 The Classification Of Redox Reactions
In the 1950s, Henry Taube identified two mechanisms of redox
reactions for metal complexes.One is the inner-sphere mechanism, which
includes atom-transfer processes. In aninner-sphere mechanism, the
coordination spheres of the reactants share a ligand transitorilyand form a
bridged transition state. The other is an outer-sphere mechanism,
whichincludes many simple electron transfers. In an outer-sphere
mechanism, the complexescome into contact without sharing a bridging
ligand and the electron tunnels from one metal atom to the other.
3.4 Outer Sphere Electron-Transfer
In principle outer sphere mechanism involves electron transfer
from reductant to oxidant with the coordination shells or spheres of each
staying intact. That is one reactant becomes involved in the outer or
second coordination sphere of the other reactant and an electron flows
from the reductant to oxidant. Such a mechanism is established when
rapid electron transfer occurs between two substitution-inert complexes.
No sharing of ligands and occurs when redox is faster than ligand
substitution. The key to the mechanism is the matching of the energies of
the reactants. i.e., the electron transfer should be between the same
energies of reactants, so that electrons do not have to move (Frank-
Condon Principle).In an outer-sphere mechanism, electron transfer
occurswithout a covalent linkage being formed between thereactants.
37
To Enhance Outer-Sphere Electron Transfer Rates
Complementary Reactions 1.Minimal solvent reorganisation (large ligands)
2. Small changes in M-L bond length
3. Good orbital overlap.
NOTES
Two examples.
Mechanism
Electron transfer from the reductant to the oxidant, with the coordination
shells or spheres of eachstaying intact. (One reactant becomes involved
with outer sphere or second coordination sphereof the other
reactant).Such reactions are observed in electron-transfer reactions of
substitutionally inert complexes
Step 1.Formation of the Precursor Complex.This step is always

considered to be fast,
Step 2.Chemical Activation and Electron Transfer.Chemical activation of

the precursor and
electron transfer and relaxation of the successor complex. Dissociation to
the separated products.
Here kobs = KAkel.
An outer sphere electron transfer rate of 1.1 M -1 sec-1, simply requires the
transfer of electron
from eg orbital of one Co to the other.
38
Unit -4 Spectral
properties of
complexes
The reaction is very slow k = 10 -9 M-1 sec-1 requires a change of spin

multiplicity as well. NOTES
In addition the oxidant and reductant must structurally reorganise

themselves before electrontransfer so that the energies of their transition
states are equal.
Marcus-Hush equation K12 = (k11 k22 K12 f12)

Where k = rate constants, K12= equilibrium constant for cross-reaciton,
Log f = (logK12)2/4logk11k22/Z2)
Z = effective collision frequency in solution
If the value of k12 calculated from the Marcus-Hushequation agrees with

the experimental value, thisprovides strong evidence that the cross-
reactionproceeds by an outer-sphere mechanism.If the Marcus-Hush
equation is not fullfilled, thisindicates that another mechanism (e.g.
inner-spheremechanism) is probably operative.
From thermodynamics, Driving force ∆Go = -nF∆E0
39
Complementary and Non- 3.5 Inner Sphere Electron Transfer
Complementary Reactions An inner sphere mechanism is one in which the reactant and oxidant
share a ligand in their inneror primary coordination spheres the electron
being transferred across a bridging group.In an inner-sphere mechanism,
electron transfer occursvia a covalently bound bridging ligand.
NOTES
Reduction of hexaamminecobalt(3+) by hexaaquochromium(2+) occurs

slowly (k = 10-3 M-1 sec-1) byan outer sphere mechanism.
However, if one ammonia ligand on Co(III) is substituted by Cl-, reaction

now occurs with a
substantially greater rate (k = 6 x 105 M-1 sec-1)
One reactant (usually the oxidant) possesses at least one ligand capable
of binding simultaneouslyto two metal ions.The other reactant is
substitutionally labile; i.e. one ligand must be replaced by the
bridgingligand.Ligand transfer is not a requirement for inner sphere
mechanism.
Steps and Rate Expression for the Inner Sphere Mechanism
1. Formation of a precursor complex (bridge formation)
2. Activation of the precursor, and electron transfer via bridge
3. Dissociation to the separated products
The overall reaciotn can be given by

k1 k3
Ox-X + Red [Ox-X -Red] Ox- + Red+
k2 k4
k1k3 40
Self-Instructional Material kobs = [Ox-X][ Red]
k2+k3
k1 is rate limiting, formation of the precursor complex (usually
substitution of the bridging ligandfor H2O on the Red complex).k3 is rate
determining, electron transfer within the complex, or fission of the Unit -4 Spectral
successor complex.Both extremes give 2 order kinetics. Most inner- properties of
complexes
sphere processes exhibit second orderkinetics.Any of the three steps
(bridge formation, electrontransfer, bridge cleavage) can be rate-
determining.
If the reaction is carried out in the presence of free *Cl,labelled Cl NOTES
is not incorporated into the product complex.The transferred Cl must
have been bound to bothmetal centres during the reaction.
Common bridging ligands in inner-sphere mechanisms:halides, OH-,
CN-. NCS.
3.6 Isomerization And Racemization Of Octahedral Complexes
Tris-chelate complexes exist in enantiomeric configurations 
and  about the metal atom and when the chelating ligand is
unsymmetrical, there are also geometrical isomers, cis and trans. Each
geometrical isomer exists in enantiomeric forms; thus there are four
different molecules.
In the case of tris complexes with symmetrical ligands, the
process of inversion (interconversion of enantiomers) is of considerable
interest. When the metal ions are of the inert type, it is possible to
resolve the complex; then the process of racemization can be followed by
measurement of optical rotation as a function of time. Possible paths of
racemization fall into two broad classes, those without bond rupture and
those with bond rupture.
There are two pathways without bond rupture that have been
widely discussed. One is the trigonal, or Bailar twist and the other is
rhombic, or Ray – Dutt Twist.
Twist processes are of course, not confined to chelate complexes.
It has already been noted that some cis – M(CO)4(PR3)2 complexes are
believed to isomerize in this way.
To illustrate the approach, let us consider some of the data and
deductions for the system Co[CH3COCHCOCH(CH3)2]3 measured in
C6H5Cl. It was found that both the isomerization and the racemization are
intramolecular processes, which occur at approximately the same rate
and with activation energies that are identical within experimental errors.
It thus appears likely that the two processes have the same transition
state. This excludes the twist mechanism as the principal pathway for
racemization.
Moreover, it was found that isomerization occurs mainly with
inversion of configuration. This imposes a considerable restriction on the
acceptable pathways. Detailed consideration of the stereochemical
consequences of the various dissociative pathways, and combinations
thereof, leads to the conclusion that for this system the major pathway is
through a tbp intermediate with the dangling ligand in an axial position.
41
Evidence for the trigonal twist mechanism has been obtained in a
Complementary Reactions few complexes in which the ―bite‖ of the ligand is small, thus causing the
ground state configuration to have a small twist angle . A twist
Mechanism is preferred in these cases because the structure is distorted
away from an octahedral configuration of sulfur atoms towards a trigonal
prismatic configuration. Thus the transition state, which is trigonal
NOTES prismatic, is probably more energetically accessible than it would be if
the complex had an essentially regular octahedral ground configuration.
The three possible modes of intramolecular racemization of a trischelate
complex.
Example :Octahedron is stereochemically rigid, loss of a ligand gives a
5-coordinate species which can undergo Berry pseudorotation.
If the lifetime of the intermediate is long enough, it provides a

mechanism for isomerization,
3.7 Template Effect and Synthesis of Macrocyclic Ligands

Template reactions are those in which formation of a complex
places the ligands in the correct geometry for reaction. One of the earliest
was for the formation of phthalocyanines..Phthalic acid and ammonia
first form phthalimide, then 1-keto-3-iminoisoindoline, andthen 1-amino-
3-iminoisoindolenine. The cyclization reaction then occurs, probably
with theassistance of the metal ion, which holds the chelated reactants in
position. This is confirmedby the lack of cyclization in the absence of the
metals. The essential feature of these reactionsis the formation of the
cyclic compound by coordination to a metal ion.
42
Unit -4 Spectral
properties of
complexes
NOTES
Phthalocyanine synthesis
A major feature of template reactions is that formation of the

complex brings the reactantsinto close proximity with the proper
orientation for reaction. Complexation also changes theelectronic
structure to promote the reaction. Both features are important in all
coordinatedligand reactions, but the orientation factor is more obvious
because the final product has astructure determined by the coordination
geometry.
N
H2 N CHO
S N S N
Ni Ni
N S N S
H2
N
SH S SH
+
CH N HC N
O
NH2 N N N
H
Schiff Base Template Reaction.

(a) The Ni(II)- o –aminothiophenol complex reacts with pyridine-1-carboxaldehyde to
form the Schiff base complex.
(b) In the absence of the metal ion, the product is benzothiazoline; very little of the
Schiff base is formed.
Synthesis of Macrocyclic ligands
Macrocycles that are saturated or have double bonds in only one
part of the ring can be made independently or can be made by template
synthesis where the presence of a metal ion controls the ligands
synthesis. An important route is the Schiff base condensation reaction.
43
1 1
R R
O + 3 N + H2O
Complementary and Non- 2
RNH2 2
R R 3
Complementary Reactions R
H2 H2 H
N N N N
Ni2+ + 4 Me2CO Ni2+
N N N N
H2 H2
H
NOTES
H2 H2 H
N N N N
2+ + 2Me2CO 2+
Cu Cu
N N N N
H H
The condensation of O-aminothiophenol with pyridine – 1 –

carboxaldehyde gives benzthiaazoline in the absence of metal ions.
SH S SH
+
CH N HC N
O
NH2 N N N
H
In the presence of metal ions, any small amount of the Schiff base that
may be in equilibrium with benzthiazoline will be removed to give a
metal complex
2. The self condensation of o-amino benzaldehyde in the presence of
BF3.OEt2 in acetic acid gives a macro cycle and when metal ion is also
present, a complex is formed.
CHO
M2+ N N
M
NH2 N N
3. The reaction of chelate complexes as follows

CH3 H3C
H2 H2
N N R CH3
HN Ni2+ NH N N R
N N +
O O Ni2+
N N
+
R N N
+
R R
N S Br N S
Ni + Ni
N S Br N S
R R

1. What is meant by complementary reactions and non-complementary
reactions?
44
2. Define Inner-sphere mechanism.
3. Define Outer-sphere mechanism.
4. What is meant by racemization and isomerization? Unit -4 Spectral
5. Define template effect. properties of
complexes
3.9 Answers To Check Your Progress Questions
1. Redox reactions in which the oxidant and reductant change their
oxidation states by an equal number of units are called complementary
reactions. Non- complementary reactions proceed through multistep, NOTES
each step involving a single electron transfer in which the intermediates
of unstable oxidation states are formed.
2. In an inner-sphere redox reaction a ligand is shared to form a transition
state; in an outersphereredox reaction there is no bridging ligand between
the reacting species.The rate-determining step of an inner-sphere redox
reaction may be any one of the componentprocesses, but a common one
is electron transfer.
3. An outer-sphere redox reaction involves electron tunnelling between
two reactants without any major disturbance of their covalent bonding or
inner coordination spheres; the rate constant dependson the electronic
and geometrical structures of the reacting species and on the Gibbs
energy of reaction.
4.Isomerization reactions are closely related to substitution reactions;
indeed, a major pathway for isomerization is often via
substitution.Isomerization of a complex can take place by mechanisms
that involve substitution, bondcleavage, and reformation, or twisting.
5. Template reactions are those in which formation of a complex places
the ligands in the correct geometry for reaction. A major feature of
template reactions is that formation of the complex brings the
reactantsinto close proximity with the proper orientation for reaction.
Complexation also changes theelectronic structure to promote the
reaction. Both features are important in all coordinatedligand reactions,
but the orientation factor is more obvious because the final product has
astructure determined by the coordination geometry.
3.9 Summary
 Redox reactions in which the oxidant and reductant change their
oxidation states by an equal number of units are called
complementary reactions.
 Non-complementary reactions proceed through multistep, each
step involving a single electron transfer in which the
intermediates of unstable oxidation states are formed.
 In an inner-sphere redox reaction a ligand is shared to form a
transition state; in an outersphereredox reaction there is no
bridging ligand between the reacting species.
 An outer-sphere redox reaction involves electron tunnelling
between two reactants without any major disturbance of their
45
covalent bonding or inner coordination spheres; the rate constant
Complementary Reactions dependson the electronic and geometrical structures of the
reacting species and on the Gibbs energy of reaction.
 Isomerization reactions are closely related to substitution
reactions; indeed, a major pathway for isomerization is often via
substitution.
NOTES  Template reactions are those in which formation of a complex
places the ligands in the correct geometry for reaction. A major
feature of template reactions is that formation of the complex
brings the reactantsinto close proximity with the proper
orientation for reaction.
3.10 Keywords
 Complementary reactions - Redox reactions in which the oxidant &
reductant change their oxidation states by an equal number of units.
 Outer-sphere mechanism - Reaction involves electron tunnelling
between two reactants without any major disturbance of their
covalent bonding or inner coordination spheres.
 Template effect -A metal ion can be used to assemble a group of
ligands which undergoes a reaction among themselves to form a
macrocyclic ligand, acyclic molecule with several donor atoms. This
phenomenon is known as template effect.
1. Give the difference between complementary reactions and non-
complementary reactions.
2. Give a brief review about inner-sphere mechanism.
3. Give a brief review about outer-sphere mechanism.
4. Explain about isomerization reactions.
5. What is template effect?
6. Give a detailed picture about the synthesis of macrocyclic ligands.
2. Gary L. Miessler., Paul J. Fischer., Donald A. Tarr. Inorganic
Chemistry, 5th edition : Pearson
3. Shriver and Atkins., Inorganic Chemistry, 5th ed : W. H. Freeman
4. Cotton, F.A. and G. Wilkinson. 1988. Advanced Inorganic
Chemistry, 5th Edition. New Jersey: Wiley Eastern.
5. Ajai kumar.2014, Coordination chemistry, 2nd edition: Aaryush
educations.
46
BLOCK 2 SPECTRAL PROPERTIES OF
Spectral properties of complexes
COMPLEXES, SPINELS, CAGES,
CLUSTERS AND BORANES
UNIT 4 SPECTRAL PROPERTIES OF COMPLEXES
Structure NOTES
4.0 Introduction
4.1 Objectives
4.2.2 Russel-Saunders or L-S coupling
4.2.3 Term state for d ions in Octahedral complexes
4.3.2 Orgeldiagrams
4.6 Summary
4.7 Keywords
4.0 Introduction
Electronic spectra of coordination compounds
Explanation of electronic spectra of transition metal complexes,
could become possible only after developments of CFT. Which
considered splitting of a d-atomic orbitals of transition metal ions, after
complex - formation. This splitting, and hence splitting energy was
considered responsible for the visible and ultra-violet spectra of transition
metal complexes. However, the detailed explanation of transition metal
complex-spectra is obtained, with the knowledge of molecular orbitals of
metal complexes. The bands obtained in the electronic spectra of
transition metal complexes are considered to be due to transition of
electrons from one d atomic orbital to the other d orbital (d – d
transitions).
47
Many transition metal complexes are colored. This is due to
transitions of electrons between the molecular orbitals that are formed
Spectral Properties of Complexes largely by the d orbitals on the metal. Many transitions are in the visible
range, with the color of the complex taking on the complementary color
of the frequency or frequencies absorbed.
Absorption of light occurs when electrons are promoted from lower to
NOTES higher energy states. An interaction between electrons causes more than
one peak in the UV/Vis spectra of these complexes. The electrons are
not independent of each other, and the spin angular momenta and orbital
angular momenta interact.
Absorption of radiation leading to electronic transitions within a
molecule or complex. The UV/Vis spectra are used to determine the
value of ∆ o for the complex. The spectra arise from electronic transitions
between the t2g and eg set of molecular orbitals. Electron-electron
interactions can greatly complicate the spectra. The interaction of orbital
angular momenta (ml values) and spin angular momenta (ms values) is
called Russel-Saunders or LS coupling. The lower transition metals (4d
and 5d) undergo further coupling (called j-j coupling or spin-orbit
coupling).
Absorption bands in electronic spectra are usually broad, and occur much
more rapidly than molecular vibrations. As a result, the spectra represent
a ―snapshot‖ of molecules in various vibrational and rotational states.
Extinction coefficients will range from <1 up to 50,000 M-1cm-1
depending upon the type of electronic transition and whether it is
permitted based on selection rules.
4.1 Objectives
The main aim of this unit is to see how to analyse the electronic spectra
of transition metal complexes, and hence to enrich our understanding of
their bonding. After going through this unit you should be able to :
 describe spectroscopic ground states and their correlation;
 calculate values of dq, B and B` parameter considering the bands
obtained in the spectra of the complex;
 explain charge transfer spectra (both the metal to ligand, and
ligand to metal charge transfer); and
 Explain the microstate and term symbol
 Explain the selection rule for electronic spectrum
 Draw the Orgel and Tanabe –Sugano diagrams
Spectra are broadly classified into two groups
(i) Emission spectra and (ii) Absorptionspectra
i. Emission spectra:Emission spectra are of three kinds
(a) continuous spectra,
(b) bandspectra and
(c) line spectra.
48
Continuous spectra: Solids like iron or carbon emit continuous spectra
when they are heateduntil they glow. Continuous spectrum is due to the
thermal excitation of the molecules of the substance.
Band spectra: The band spectrum consists of a number of bands of
different colours separatedby dark regions. The bands are sharply defined
at one edge called the head of the band andshade off gradually at the
other edge. Band spectrum is emitted by substances in themolecular state
NOTES
when the thermal excitement of the substance is not quite sufficient to
breakthe molecules into continuous atoms.
Line spectra: A line spectrum consists of bright lines in different regions
of the visiblespectrum against a dark background. All the lines do not
have the same intensity. The number of lines, their nature and
arrangement depends on the nature of the substanceexcited.
Line spectra are emitted by vapours of elements. No two elements do
ever producesimilar line spectra.
ii. Absorption spectra: When a substance is placed between a light

source and aspectrometer, the substance absorbs certain part of the
spectrum. This spectrum iscalled the absorption spectrumof the
substance.
Beer-Lambert Law
The absorption at any wavelength obeys the Beer-Lambert Law:
A = log(Io/I) = εcb; where A = absorbance, Io = incident light
intensity
I = transmitted light intensity, ε = molar absorptivity at a
particular wavelength
c = molar concentration, b = path length through the absorbing
medium
It should be mentioned that not all bands in the visible and ultraviolet
spectra of transition metal complexes are d – d spectra. Some arise from
electron transfer (may be in either direction) between metal ion and
ligand. Such charge transfer spectra are of high intensity and usually
occur at somewhat higher frequency than d-d transition. Generally,
electronic spectra are of four types :
The d-d or Ligand Field Spectra
This occurs in the near infrared, visible, and ultraviolet regions. Lower
frequencies are not accessible experimentally; the higher frequencies
though accessible, are overshadowed by the charge transfer and the
interligand transitions. This limits the study of the d-d transitions to only
the visible regions of spectrum. These transitions are considered to be
totally within the metal ion in the CFT model, though some ligand
contribution is included in LFT or ACFT models. MOT treats these
transitions as arising due to the excitation of the electron from the t 2g
level to eg* levels belonging largely to the metal itself.
49
Ligand-to-Metal Charge Transfer Bands
When the electron transition takes place from a MO located primarily on
Spectral Properties of Complexes the ligand (M – L bonding  or  orbitals) to a nonbonding or
antibonding MO located primarily on the metal atom, the ligand-to-metal
charge transfer bands are observed. These cannot be explained by CFT
and represent the tendency of ligands to reduce the metal ion. The
NOTES semiempiral MOT is adequate for explaining it.
Metal-to-Ligand Charge Transfer Bands
These involve the transition of electron from an antibonding or non-
bonding orbital, concentrated on the metal atom, to the antibonding
orbital located primarily on the ligand, and measures the tendency of the
metal ion to reduce the ligand. These bands are observed generally for
the metal ions in low oxidation states in the ultraviolet region, but are
seen many times to tail into the visible regions, e.g. [Fe (dipy)3]2+.
The Intraligand Transitions
When an electron transition takes place from one ligand orbital to another
ligand orbital, the intraligand transitions are observed. They are found in
the ultraviolet regions and can be readily separated from the equally
intense M – L charge transfer bands as they are not affected much by the
other ligands. They, however, depend on the M – L bond strength.
Franck-Condon Principle: Electronic transitions occur in a very short
time (about 10-15sec.) and hence the atoms in a molecule do not have
time to change position appreciably during electronic transition.So the
molecule will find itself with the same molecularconfiguration and hence
the vibrational kinetic energy in the exited state remains thesame as it
had in the ground state at the moment of absorption.
Electronic transitions between vibrational states: Frequently, transitions

occur from theground vibrational level of the ground electronic state to
many different vibrational levelsof particular excited electronic states.
Such transitions may give rise to vibrational finestructure in the main
peak of the electronic transition. Since all the molecules are presentin the
ground vibrational level, nearly all transitions that give rise to a peak in
theabsorption spectrum will arise from the ground electronic state. If the
different excitedvibrational levels are represented as υ 1, υ2, etc., and the
ground state as υ0, the fine structurein the main peak of the spectrum is
assigned to υ0 → υ0, υ0 → υ1, υ0 → υ2 etc., vibrationalstates. The υ0 → υ0
transition is the lowest energy (longest wave length) transition.
Electronic transitions occur between split‗d‘ levels of the central atom

giving rise to socalled d-d or ligand field spectra.
The spectral region where these occur spans the near
Ultraviolet (UV) Visible (Vis) Near infrared (NIR)
50,000 - 26300 26300 -12800 12800 -5000cm-1
200 - 380 380 -780 780 - 2000 nm
50
4.2.2 Russel-Saunders or L-S coupling Spectral properties of complexes
An orbiting electronic charge produces magnetic field
perpendicular to the plane of theorbit. Hence the orbital angular
momentum and spin angular momentum havecorresponding magnetic
vectors. As a result, both of these momenta couple magnetically togive
rise to total orbital angular momentum. There are two schemes of
NOTES
coupling: Russel-Saunders or L-S coupling and j-j coupling.
4.2.3 Term state for d ions in octahedral complexes
In quantum mechanics, the term symbol is an abbreviated
description of the (total) angular momentum quantum numbers in a
multi-electronatom. Each energy level of an atom with a given electron
configuration is described by not only the electron configuration but also
its own term symbol, as the energy level also depends on the total
angular momentum including spin. The usual atomic term symbols
assume LS coupling (also known as Russell–Saunders coupling or spin–
orbit coupling). The ground state term symbol is predicted by Hund's
rules.
Atomic states are then well described by term symbols of the

2S+1
form LJ
S is the total spin quantum number. J is the total angular momentum
quantum number.2S + 1 is the spin multiplicity, which represents the
number of possible states of J for a given L and S, provided that L ≥ S. (If
L<S, the maximum number of possible J is 2L + 1).
This is easily proven by using Jmax = L + S and Jmin = |L − S|, so that the
number of possible J with given L and S is simply Jmax − Jmin + 1 as J
varies in unit steps.L is the total orbital quantum number in spectroscopic
notation. The first 17 symbols of L are:
L = 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 ...
(continued
SPDFGHI KLMN O Q R T U V
alphabetically)
The nomenclature (S, P, D, F) is derived from the characteristics of the

spectroscopic lines corresponding to (s, p, d, f) orbitals: sharp, principal,
diffuse, and fundamental.
The rules governing the term symbol for the ground state
according to L-S coupling schemeare given below:
1. The spin multiplicity is maximized i.e., the electrons occupy
degenerate orbitals so as toretain parallel spins as long as possible
(Hund‘s rule).
51
2. The orbital angular momentum is also maximized i.e., the orbitals are
filled withhighest positive m values first.
Spectral Properties of Complexes 3. If the sub-shell is less than half-filled, J = L– S and
if the sub-shell is more than half –filled, J = L +S.
It should be notedthat S is used to represent two things-

NOTES
(a) total spin angular momentum and (b) and totalangular
momentum when L = 0.
The above rules are illustrated with examples.
J = 3-1 =2; 3F2
For d4 configuration
ml +2 +1 0 -1 -2
Hence, L = 3 -1 = 2 i.e., D;
S = 2; 2S+1 = 5;
and J = L- S = 2-2 = 0;
Term symbol = 5D0
J =
L+S =
0+5/2;6S5/2
For d9 configuration
ml +2 +1 52 0 -1 -2
Hence, L = +2+2+1+1+0+0-1-1-2 = 2 i.e., D ; Spectral properties of complexes
S = 1 /2 ; 2S+1 = 2 ;
and J = L+ S = 3/2 ; Term symbol = 2D5/2
NOTES
1
S0 (singlet S nought); 2S1/2 (doublet S one–half); 3P2 (triplet P two );
5
I8(quintet I eight).
d electrons are only of importance in deciding term symbols of
transitionmetals.

The electrons may be filled in orbitals by different arrangements since
the orbitals havedifferent ml values and electrons may also occupy singly
or get paired. Each different typeof electronic arrangement gives rise to a
microstate. Thus each electronic configuration willhave a fixed number
of microstates. The numbers of microstates for p 2 configuration aregiven
in Table (for both excited and ground states).
The number of microstates possible for any electronic configuration may
be calculated from
the formula,Number of microstates = n! / r! (n - r)!
Where n is the twice the number of orbitals, r is the number of electrons
and !is the factorial.
For p2 configuration, n= 3x2 =6; r = 2; n – r = 4
6! = 6 x 5 x 4 x 3 x 2 x 1 = 720; 2! = 2 x 1 =2; 4! = 4 x 3 x 2 x 1 = 24
Substituting in the formula, the number of microstates is 15.
ml
-1
0
+1
ML +1 0 -1 +1 0 -1 +1 0 -1 +1 +1 -1 +2 0
53
Number of microstates for p2 configuraion Self-Instructional Material
Spectral Properties of Complexes
Similarly for a d2 configuration, the number of microstates is given by
10! / 2! (10 – 2)!
10 x 9 x 8 x 7 x 6 x 5 x 4 x 3 x 2 x 1
NOTES =45
2 x 1 (8 x 7 x 6 x 5 x 4 x 3 x 2 x 1)
Thus a d2 configuration will have 45 microstates. Microstates of different

dn configurationare given in Table.
Microstates of different dn configuration
dn configuration d1 d2 d8 d3,d7 d4,d6 d5 d10
No.of microstates 10 45 120 210 252 1
The magnitude of the extinction coefficient (intensity of the

colour) is affected by two quantum mechanical selection rules that state
whether transitions are allowed (intense colour) or forbidden (pale
colour).
 Spin selection rule–the number of unpaired electrons in a
molecule cannot change upon excitation (i.e., an electron ―spin-
flip‖ is forbidden).
ΔS = 0
2S→ 2P and 3D→ 3P are allowed, but transition such as 1S→ 3P
isforbidden.
-Transitions may occur from singlet to singlet, or from triplet

totriplet states etc., but a change in spin multiplicity is forbidden.
S = 0, spin-allowed transitionstransition between states of same

spin multiplicity
S ≠ 0, spin-forbidden transitionstransition between states of
different spin multiplicity
54
 Symmetry selection rule -Laporte selection rule; if the molecule
has a center of symmetry (inversion center), transitions from one
centrosymmetric orbital to another are forbidden (i.e., all d
orbitals are centrosymmetric, so d-d transitions are forbidden in a
complex that has an inversion center. If the molecule does not NOTES
have an inversion center, d-d transitions are symmetry allowed).
This means that all d-d transitions in octahedral complexes areformally

forbidden as there is center of symmetry
Hence all d-d transitions in octahedral complexes are weak
– For tetrahedral complexes there is no center of symmetry are typically
stronger than thosein octahedral complexes
Laporte selection rule: There must be a change in parity:
1S→ 1P and 2D→ 2P are allowed but transition such as3D→ 3S is
forbidden since Δ L = -2
allowed transitions: g ↔ u
forbidden transitions: g ↔ g , u ↔ u
This leads to the selection rule:ΔL = ±1
allowed transitions are: s → p, p→ d, d → f,
forbidden transitions are: s → s, p → p, d → d, f → f, s → d, p → f,

Spin-orbit coupling
For electronic transition to take place, Δ S = 0 and Δ L= ± 1 in the
absence of spin-orbit coupling.However, spin and orbital motions are
coupled. Even, if they are coupled very weakly, a little ofeach spin state
mixes with the other in the ground and excited states by an amount
dependentupon the energy difference in the orbital states and magnitude
of spin –orbit coupling constant.Therefore electronic transitions occur
between different states of spin multiplicity and alsobetween states in
which Δ L is not equal to ± 1. For example, if the ground state were
99%singlet and 1% triplet (due to spin– orbit coupling) and the excited
state were 1% singlet and 99% triplet, then the intensity would derive
from the triplet –triplet and singlet-singletinteractions. Spin-orbit
coupling provides small energy differences between degenerate state.
55
La Porte selection rule
Physically 3d (even) and 4p (odd) wave functions may be mixed,
Spectral Properties of Complexes
if centre of inversion (i) isremoved.
The central metal ion is placed in a distorted field (tetrahedral
field, Tetragonaldistortions, etc.,) The most important case of distorted or
NOTES asymmetric field is the case ofa tetrahedral complex. Tetrahedron has no
inversion centre and so d-p mixing takesplace. So electronic transitions in
tetrahedral complexes are much more intense, oftenby a factor 100, than
in a analogous octahedral complexes. Trans isomer of [Co(en) 2Cl2]+in
aqueous solution is three to four times less intense than the cis isomer
because theformer is centro-symmetric. Other types of distortion include
Jahn –Teller distortions.
Odd vibrations of the surrounding ligands create the distorted
field for a time that is longenough compared to the time necessary for the
electronic transition to occur (FranckCondon Principle).Certain
vibrations will remove the centre of symmetry. Mathematicallythis
implies coupling of vibrational and electronic wave functions. Breaking
down of LaPorte rule by vibrionic coupling has been termed as ―Intensity
Stealing‖. If the forbiddenexcited term lies energetically nearby a fully
allowed transition, it would produce a veryintense band. Intensity
Stealing by this mechanism decreases in magnitude withincreasing
energy separation between the excited term and the allowed level.
The molar absorptivity (max, extinction coefficient) is a good indicator of

the type of electronic transition
Electronic transition max Example
Laporte allowed (charge 1000—50000 Organic

transfer) chromophores,
MnO4-
Laporte forbidden (d-d 100 - 500 Most 3d Oh
transition) complexes
spin allowed; Td complexes,
noncentrosymmetiric CoCl4
spin allowed; 5—100 [Co(OH2)6]2+
centrosymmetric complexes
spin forbidden 0.01—1 [Mn(OH2)6]2+
complexes
The symbols A(or a) and B (or b) with any suffixes indicate wave
functions which are singlydegenerate. Similarly E (or e) indicates double
56
degeneracy and T (or t) indicates tripledegeneracy. Lower case symbols,
a1g, a2g, eg, etc., are used to indicate electron wavefunctions(orbitals) and Spectral properties of complexes
upper case symbols are used to describe electronic energy levels.Thus
2
T2g means an energy level which is triply degenerate with respect to
orbital state andalso doubly degenerate with respect to its spin state.
Upper case symbols are also usedwithout any spin multiplicity term and
they then refer to symmetry (ex., A1g symmetry). Thesubscripts g and u NOTES
indicate gerade(even) and ungerade(odd).d orbitals split into two sets -
t2g orbitals and eg orbitals under the influence crystal field.These have T 2g
and Eg symmetry respectively.
Energy Level Diagrams are described by two independent schemes -
Orgel Diagrams whichare applicable to weak field complexes and
Tanabe –Sugano (or simply T-S) Diagramswhich are applicable to both
weak field and strong field complexes.
4.3.2 Orgel Diagrams
Orgel Diagrams are correlation diagrams which show the relative
energies of electronic terms in transition metal complexes that shows
how ligand field strength affects the energy of the crystal field terms.
They are named after their creator, Leslie Orgel. Orgel diagrams are
restricted to weak ligand fields of both octahedral (Oh) and tetrahedral
(Td) complexes (i.e. high-spin complexes). Because Orgel diagrams are
qualitative, no energy calculations can be performed from these
diagrams. Orgel diagrams only show the symmetry states of the highest
spin multiplicity instead of all possible terms, unlike a Tanabe-Sugano
diagram. Orgel diagrams will, however, show the number of spin allowed
transitions, along with their respective symmetry designations. Orgel
diagrams are for qualitative purposes only. Tanabe-Sugano diagrams
must be used for low-spin cases and any spin-forbidden transitions (high-
spin or low-spin).
In an Orgel diagram, the parent term (P, D, or F) in the presence
of no ligand field is located in the center of the diagram, with the terms
due to that electronic configuration in a ligand field at each side. There
are only two Orgel diagrams, one for d1, d4, d6, and d9 configurations and
the other with d2, d3, d7, and d8 configurations. Only terms with same
multiplicity as the ground state are shown because only these can be
involved in transition from the ground state (spin selection rule).
Remember that d1 Td splitting is just the opposite of d1 Oh, so d1 Td and
d9 Oh have similar Orgel Diagrams; same with d9 Td and d1 Oh.In an
Orgel diagram, energy is represented as the vertical dimension, and the
vertical line in the centerof the diagram represents the gaseous ion where
there is no ligand fi eld( Δ0). Note that theright-hand side of the diagram
applies to d1 and d6 ions in octahedral fields or d4 and d9 ions in
tetrahedralfields. This situation arises because the ligand fi eld states are
inverted for the two cases, and theelectron-hole formalism also causes the
57
orbitals to be inverted. As a result, the ligand field states are the same for
a d1 ion in an octahedral field as they are for a d4 ion in a tetrahedral
Spectral Properties of Complexes field.
NOTES
An Orgel diagram for metal ions having D spectroscopic ground states.

The multiplicity of the D state is not specified because it isdetermined by
the number of electrons in the d orbitals of the metal ion.
• First look at splitting of the ground state, 3F term as we move

from a spherically symmetric to octahedral (or tetrahedral) field.
• Next, add 3P component in octahedral field, 3T1g.
• Note that there is a problem on the left hand side of the diagram
as two 3T1g components are crossing. As we saw with MO
diagrams, two energy components with identical symmetry will
mix rather than cross.
• So, the predicted transitions would be: T1g → T2g, T1g → T1g (P)
and T1g → A2g. However, this last transition would involve the
simultaneous excitation of two electrons and so is relatively
impossible; for d8 Oh all 3 transitions are possible.
• Although Orgel Diagrams are good for qualitatively predicting
transitions, they are not good for predicting 10Dq value, nor do
they account for high spin /lowspin.
58
An Orgel diagram for metal ions having F spectroscopic ground states. Spectral properties of complexes
The multiplicity of the F state is not specified.The P state having the

same multiplicity as the ground state is also shown.

The inter-electronic repulsions within a configuration are linear NOTES
combinations of Coulombicand exchange integrals above the ground
term. They are expressed by either of the twoways: Condon - Shortley
parameters, F0, F2 and F4 and Racah parameters, A, B and C.
Themagnitude of these parameters varies with the nature of metal ion.
The Racah parameters are A, B and C. The Racah parameter A
corresponds to the partialshift of all terms of a given electronic
configuration. Hence in the optical transitionconsiderations, it is not
taken into account. The parameter, B measures the inter-
electronicrepulsion among the electrons in the d-orbitals. The decrease in
the value of theinterelectronic repulsion parameter, B leads to formation
of partially covalent bonding.The ratio between the crystal B 1parameter
and the free ion B parameter is known asnephelauxeticratio and it is
denoted by β. The value of β is a measure of covalency. Thesmaller the
value, the greater is the covalency between the metal ion and the ligands.
TheB and C values are a measure of spatial arrangement of the orbitals of
the ligand and themetal ion.
Racah redefined the empirical Condon –Shortley parameters so
that the separation betweenstates having the maximum multiplicity (for
example, difference between is a function of 3Fand 3P or 4F and 4P is a
function of a single parameter, B. However, separations betweenterms of
different multiplicity involve both B and C.

Exact solutions for the excited sate energy levels in terms of Dq,
B and C are obtained from Tanabe-Sugano matrices. The T-S diagrams
are valid onlyif the value of B, C and Dq are lower for a complex than for
the free ion value.Quantitative interpretation of electronic absorption
spectra is possible by using Tanabe –Sugano diagrams or simply T-S
diagrams. These diagrams are widely employed to correlateand interpret
spectra for ions of all types, from d2 to d8. Orgel diagrams are useful
onlyqualitatively for high spin complexes whereas T-S diagrams are
useful both for high spinand low spin complexes. The x-axis in T-S
diagrams represent the ground state term.Further, in T-S diagrams, the
axes are divided by B, the interelectronic repulsion parameteror Racah
Parameter. The x-axis represents the crystal field strength in terms of Dq/
59
B or Δ / Band the Y-axis represents the energy in terms of E/B.The
energies of the various electronic states are given in the T-S diagrams on
Spectral Properties of Complexes the verticalaxis and the ligand field strength increases from left to right
on the horizontal axis. Thesymbols in the diagram omit the subscript, g,
with the understanding that all states aregeradestates. Also, in T.S.
diagrams, the zero of energy for any particular d n ion is taken tobe the
NOTES energy of the ground state. Regardless of the ligand field strength, then,
thehorizontal axis represents the energy of the ground state because the
vertical axis is in unitsof E/B and x-axis is also in units of Δ /B. Thus, the
unit of energy in T-S diagram is B, RacahParameter.The values of B are
different for different ions of the same dn Configuration which is shown
on the top of each diagram. One T-S diagram is used for all members of
anisoelectronic group. Also some assumption is made about the relative
value of C/B.
It is used for the interpretation of the spectra. Tanabe-Sugano diagrams
are similar to orgel diagrams that they depict variation of the term
energies with field strength, but they differ in following aspects, .
60
NOTES
Simplified Tanabe-Sugano diagrams for d nmetal ions in octahedral

fields. The drawings have been simplified by omitting severalstates that
have multiplicities that do not permit spin allowed transitions.
f-f Transitions
f-f transitions in lanthanide complexes are weak and sharp and
have energies close to thoseexpected for free lanthanide ions. Together
with the magnetic properties, this confirms that 4forbitals have very little
overlap with surrounding atoms. High-resolution spectra measured in
crystals at low temperatures do show small ligand field splittings but they
are small (of the orderof 10cm-1) compared with splittings in transition
metal complexes.Actinides show larger ligand field effects than
lanthanides, especially ions early in the series (e.g.U 4+). The
interpretation of spectra is complicated by strong spin-orbit splitting.f-f
transitions in centrosymmetric complexes are Laporte forbidden as with
d-d spectra. Intensitiesare in the order 4f < 5f < d reflecting the order of
strength of metal-ligand interactions.
Charge Transfer Spectra
All electronic transition between orbitals that are centered on different
atoms is called a charge-transfer transition and the absorption band is
usually very strong.
61
Two types of the charge transfer (CT) bands appear in the metal
complexes:
Spectral Properties of Complexes (1) The LM CT bands as shown by oxide, chloride bromide and iodide
complexes. For d0 ions, where the d-d transitions are not possible, the CT
bands are used for the determination of the 10Dq values.
NOTES (2) The ML CT bands that occur in the acceptor ligands (CO, NO,
CN-) containing empty low energy orbitals. As the CT bands are neither
multiplicity forbidden, nor Laporte forbidden, they have high absorption
intensities (50-2001 mm-1 mol-1).
1. Explain term symbol
2. Define Franck-Condon Principle
3. Why tetrahedral complexes are normally bright in colour?
4. Why Au(II) is unstable?
5. Define Microstates?
6. Give formula for Spin selection rule in the electronic spectra?
 Atomic states are then well described by term symbols of the

2S+1
form LJ
 Electronic transitions occur in a very short time (about 10-15sec.)
and hence the atoms in a molecule do not have time to change
position appreciably during electronic transition.So the molecule
will find itself with the same molecularconfiguration and hence
the vibrational kinetic energy in the exited state remains thesame
as it had in the ground state at the moment of absorption.
 There is no center of symmetry and Laporte rule does not hold
good for d-dtransition.

Δ0 value is very high and increases from Cu(II) to Au(II). Further
the2Au2+convert like Au3+ + Au+
 The different ways in which electrons can occupy certain orbitals.
 ΔS = 0
4.6 Summary
The Selection Rules governing transitions between electronicenergy levels
of transition metal complexes are:
(i) ΔS = 0 The Spin RuleThe first rule says that allowed transitions must
involvethe promotion of electrons without a change in their spin.
(ii) ΔL = +/- 1 The Orbital Rule (Laporte)The second rule says that if the
molecule has a centre ofsymmetry, transitions within a given set of p or d
orbitals(i.e. those which only involve a redistribution of electronswithin a
given subshell) are forbidden.
62
d-d, these can occur in both the UV and visible region butsince they are
forbidden transitions have small intensities.
Relaxation of the Rules can occur through a) Spin-Orbit coupling - this
gives rise to weak spin forbiddenbands.b) Vibronic coupling - an octahedral
complex may haveallowed vibrations where the molecule is
asymmetric.Absorption of light at that moment is then possible.
NOTES
1. d1, d4, d6 and d9 complexes show one absorption.
2. d2, d3, d7 and d8 complexes show three absorptions, with the 3rd
peak often obscured.
3. d5complexes show very weak, sharp absorptions.
4.7 Keywords
UV/Vis spectra: UV/Vis spectra are used to determine the value of ∆ o
for the complex. are used to determine the value of ∆ o for the complex.
Charge-transfer transition: All electronic transition between orbitals
that are centered on different atoms is called a charge-transfer transition
and the absorption band is usually very strong.
Term symbols: Atomic states are then well described by term symbols
of the form 2S+1LJ
Selection rule: The magnitude of the extinction coefficient (intensity of
the colour) is affected by two quantum mechanical selection rules that
state whether transitions are allowed (intense colour) or forbidden (pale
colour).
Orgel Diagrams are correlation diagrams which show the relative
energies of electronic terms in transition metal complexes that shows
how ligand field strength affects the energy of the crystal field terms.
The inter-electronic repulsions within a configuration are linear
combinations of Coulombicand exchange integrals above the ground
term.
1. Define Racah parameters
2. Draw Orgel and TS diagram for d2 configuration
3. Give selection rule of Electronic spectra
4. Explain Charge-transfer transition
1. Huheey, J.E.; Keiter, E.A.; Keiter, R.L. Inorganic Chemistry:
Principles of Structure and Reactivity; 4th ed.; HarperCollins: New
York, 1993, pp. 394-408, 433-459.
2. Brisdon, A.K. Inorganic Spectroscopic Methods, Oxford University
Press: Oxford, 1998, pp. 57-73.
3. Shriver and Atkins, ―Inorganic Chemistry‖, 3/e, Oxford University
Press, 2002,
63
UNIT -5 SPINELS
Spinels
Structure
5.0 Introduction
5.1 Objective
5.2 Classification of spinels
NOTES
5.3 Normal Spinels
5.4 Inverse Spinels
5.5 Perovoskite Structure
5.6 Answer to check your progress
5.7 Summary
5.8 Keywords
5.0 Introduction
Spinel is a name of mixed ore of magnesium(Mg) and
aluminium(Al), its molecular formula is MgAlO4 (MgO.Al2O3). Here Mg
is in +2 oxidation state and Al is in +3 oxidation state.The spinels are any
class of minerals are general formation AB2X4 which crystallise in the
cubic crystal system, with the X anion arranged in a cubic close-packed
and the cations. A and B occupying some or all of the octahedral and
tetrahedral sites in the lattice. A and B can be same metal with different
valencies, as is with magnetite which is the most abundant member of the
spinel group. Spinels are grouped in series by the B cation.Spinels are
often referred to as rubies, but the ruby is not a spinel.A= any dipositive
metal (eg. Mg+2, Ni+2)
B= any tripositive metal (eg. Fe+3, Al+3, La+3).X = O, S, Se etc. ,
5.1 Objective
After going through this unit, you will be able to;
 To know the meaning of the spinels
 Understand the classification of spinels
 Discuss about the perovoskite structure
5.2 Classification of Spinels
1 Spinels aremixed oxides having formula AO.B2O3
2 They have Face Centred Cubic (CCP) structures.
3 Total No. of Atoms per unit cell = 4
4 No. of Tetrahedral (Td) voids per unit cell = 8
5 No. of Octahedral (Oh) voids per unit cell = 4
On the basis of position occupied by A+2 ions and B+3 ions,
Spinels are of two types
1. Normal Spinels
2. Inverse Spinels
5.3 Normal Spinels
The divalent A+2 ions occupy the tetrahedral voids, whereas the
trivalent B+3 ions occupy the octahedral voids in the close packed
64
arrangement of oxide ions. A normal spinel can be represented as:
(A+2)tet(B+3)2octO4 e.g. Mn3O4, ZnFe2O4, FeCr2O4
Spinels
In the normal spinel structure, there is a close-packed array of anions.
The A-site cations fill 1/8 of the tetrahedral holes and the B-site cations
fill 1/2 of the octahedral holes.
Prediction Of Structure Of Spinels:
Basic rule for determining whether a complex is Normal or Inverse Spinel,
CFSE of B+3 ions in Octahedral Feild > CFSE of B+3 ions in Tetrahedral Field NOTES
> CFSE of A+2 ions in Octahedral Field
> CFSE of A+2 ions in Tetrahedral Field
+3
i.e. if CFSE of B ions in Octahedral Feild is largest of all CFSE
For Inverse Spinel:

CFSE of A+2 ions in Octahedral Feild > CFSE of A+2 ions in Tetrahedral Feild
>CFSE of B+3 ions in Octahedral Feild
> CFSE of B+3 ions in Tetrahedral Feild
i.e. if CFSE of A+2 ions in Octahedral Feild is largest of all CFSE
A spinel unit cell is made up of 8 FCC cells. The anions (usually

oxide ions: O2-) occupy the FCC lattice points. The divalent AII cations
occupy 1/8th of the tetrahedral voids, whereas the trivalent BIII cations
occupy one half (1/2) of octahedral voids.Thus a normal spinel can be
represented as: (AII)tet(BIII)2octO4
Note: We know that in one FCC lattice unit cell, the effective numbers of
atoms (or ions) occupying the lattice points is 4. At the same time, the
effective number of tetrahedral voids (holes) = 8 and that of octahedral
voids = 4.That means, in a normal spinel, there are 8 x 4 = 32 anions
occupying the lattice points of 8 FCC unit cells. Whereas, the number of
divalent AII cations occupying tetrahedral voids is 8 x 1/8 x 8 = 8 and the
number of trivalent BIII ions occupying the octahedral voids = 8 x 1/2 x 4
= 16.i.e. The ratio of AII : BIII : O2- = 8 : 16 : 32 = 1:2:4 which confirms
with the formula of normal spinels.
5.4 Inverse Spinels
The A+2 ions occupy the octahedral voids, whereas half of B+3
ions occupy the tetrahedral voids. It can be represented as:
(B+3)tet(A+2B+3)octO4 E.g. Fe3O4 (ferrite), CoFe2O4, NiFe2O4 etc., Inverse
spinels have a closely related structure (with the same large unit cell) in
which the A-site ions and half of the B-site ions switch places. Inverse
spinels are thus formulated B(AB)O4, where the AB ions in parentheses
occupy octahedral sites, and the other B ions are on tetrahedral sites.
Many magnetic oxides, such as Fe3O4 and CoFe2O4, are spinels.
Structures of Inverse spinels (B(AB)O4): The AII ions occupy the
octahedral voids, whereas one half of BIII ions occupy the tetrahedral
65
voids and the other half occupy octahedral sites. It can be represented as:
(BIII)tet(AIIBIII)octO4.
Spinels
E.g. Fe3O4 (ferrite), CoFe2O4, NiFe2O4 etc.
The above inverse spinels can also be written as:
Fe3O4 = FeIII(FeIIFeIII)O4
CoFe2O4 = FeIII(CoIIFeIII)O4
NOTES NiFe2O4 = FeIII(NiIIFeIII)O4
The number of octahedral sites occupied may be ordered or random. The
random occupation leads to defected spinels.
E.g. NiAl2O4 for which the formula can be written as
(Al0.75Ni0.25)tet [Ni0.75 Al1.25]octaO4. Another defected spinel is γ-Al2O
Rules:
1. If both A+2 and B+3 are non transition metals then spinel will be
NORMAL.
2. If A+2 is Non transition metal and B+3 is transition metal (having
d1 d2 d3 d4 d6 d7 d8 d9) then spinel will be NORMAL.
3. If is transition metal with (d1 d2 d3 d4 d6 d7 d8 d9 ) and B is also
transition metal with (d0 d5 and d10) system then spinel will be
INVERSE
EXAMPLES FOR SPINEL AND INVERSE SPINEL
STRUCTURES
1) MgAl2O4 is a normal spinel since both the divalent and trivalent ions
are non transition metal ions. There is no question of CFSE.
2) Mn3O4 is a normal spinel since the Mn2+ ion is a high spin d5 system
with zero LFSE. Whereas, Mn3+ ion is a high spin d4 system with
considerable LFSE.
3) Fe3O4 is an inverse spinel since the Fe(III) ion is a high spin d5 system
with zero CFSE. Whereas the divalent Fe(II) is a high spin d 6 system
with more CFSE.
4) NiFe2O4 is again an inverse spinel since the divalent Ni2+ (a d8 ion)

has more CFSE than the trivalent Fe3+ (a d5 ion).
5) FeCr2O4 is a normal spinel since the divalent Fe 2+ is a high spin d6 ion

with CFSE = 4 Dq and the trivalent Cr 3+ is a high spin d3 ion with CFSE
= 12 Dq. Hence Cr3+ gets more OSSE while occupying octahedral sites.
6) Co3O4 is a normal spinel. Even in the presence of weak field oxo

ligands, the Co3+ is a low spin d6 ion with very high CFSE. It is due to
high charge on Co3+. Hence all the Co3+ ions occupy the octahedral sites.
66
NORMAL VS. INVERSE SPINEL STRUCTURE
For transition metal oxide spinels, the choice of the normal vs.
Spinels
inverse spinel structure is driven primarily by the crystal field
stabilization energy (CFSE) of ions in the tetrahedral and octahedral
sites. For spinels that contain 3d elements such as Cr, Mn, Fe, Co, and
Ni, the electron configuration is typically high spin because O2- is
a weak field ligand.As an example, we can consider magnetite, Fe3O4.
This compound contains one Fe2+ and two Fe3+ ions per formula unit, so NOTES
we could formulate it as a normal spinel, Fe2+(Fe3+)2O4, or as an inverse

spinel, Fe3+(Fe2+Fe3+)O4. Which one would have the lowest energy?
Figure: d-orbital energy diagram for Fe2+
First we consider the crystal field energy of the Fe2+ ion, which is
d6. Comparing the tetrahedral and high spin octahedral diagrams, we find
that the CFSE in an octahedral field of O2- ions is [(4)(2/5) -
(2)(3/5)]Δo - P = 0.4 Δo - P. In the tetrahedral field, the CFSE is
[(3)(3/5) - (3)(2/5)]Δt - P = 0.6 Δt - P. Since Δo is about 2.25 times larger
than Δt, the octahedral arrangement has a larger CFSE and is preferred
for Fe2+.
Figure : d-orbital energy diagram for Fe3+Fe3+

In contrast, it is easy to show that Fe3+, which is d5, would have a CFSE
of zero in either the octahedral or tetrahedral geometry. This means that
Fe2+ has a preference for the octahedral site, but Fe3+ has no preference.
Consequently, we place Fe2+ on octahedral sites and Fe3O4 is an inverse
spinel, Fe3+(Fe2+Fe3+)O4.Ferrites are compounds of general formula.
MIIFe2O4. We can see that magnetite is one example of a ferrite (with M

= Fe). Other divalent metals (M = Mg, Mn, Co, Ni, Zn) also form
ferrites. Ferrites can be normal or inverse spinels, or mixed spinels,
depending on the CFSE of the MII ion. Based on their CFSE, Fe2+, Co2+,
and Ni2+ all have a strong preference for the octahedral site, so those
67
compounds are all inverse spinels. ZnFe2O4 is a normal spinel because
the small Zn2+ ion (d10) fits more easily into the tetrahedral site than
Spinels
Fe3+ (d5), and both ions have zero CFSE. MgFe2O4and MnFe2O4, in
which all ions have zero CFSE and no site preference, aremixed
spinels. Chromite spinels, MIICr2O4, are always normal spinelsbecause
the d3 Cr3+ ion has a strong preference for the octahedral site.
NOTES
Figure: Illustration of antiferromagnetic superexchange between two

transition metal cations through a shared oxygen atom.
Factors Of Affecting Of The Structrue Of Spinels

 The relative sizes of A and B: In general, the smaller cation
prefers to occupy the site of lower coordination i.e., tetrahedral
site. However, in the spinel, MgAl2O4 itself this factor is
outweighed by greater lattice energy of smaller cation, Al3+,
which occupies the octahedral site and thus by giving normal
spinel structure. Otherwise the "spinel" will have the inverse
spinel structure!
 The Madelung constants for the normal and inverse
structures: It is observed that the Madelung constants are same
for both normal and inverse spinels and hence are not that much
important in arriving at the structure.
 Ligand-Fleld Stabilization Energies: Applicable whenever there
are transition metal ions and is discussed below.
 The structures of spinels are affected by the relative LFSE values
of metal ions. The ion with more LFSE value in octahedral
geometry when compared to the LFSE in tetrahedral geometry
tends to occupy octahedral sites.
 The difference between the LFSE values in octahedral and
tetrahedral geometries is referred to as Octahedral Site
Stabilization Energy (OSSE).
 ―If the BIII ion has more CFSE gain in octahedral site than that of
AII ion, a normal spinel is expected.‖
 ―Whereas an inverse spinel is formed whenever the divalent
AII ion has comparatively more CFSE gain in octahedral
geometry than the trivalent BIII ion.‖
68
Some Genealizations Regarding The Structrue Of Spinels
Spinels
1 A normal spinel structure is assumed if both the divalent and the
trivalent metals are non transition metals since no CFSE is
involved.
2 There is a tendency of formation of inverse spinel structure in
some cases (not all the cases) which contain transition metal ions. NOTES
This is because, the transition metal ion may get extra stability
(LFSE) in octahedral geometry, prefers octahedral voids over
tetrahedral ones.
3 The d0 ; high spin d5, d10 ions have no preference between
tetrahedral and octahedral coordination since the LFSE is zero.
4 Usually d3 & d8 ions have strongest preference for octahedral
geometry.
5 Other ions with d1, d2, d4, d6, d7, d9 too have slightly more
preference for octahedral symmetry.
6 That means, if AII has d3 or d8 configuration and the BIII ion has
configuration other than these, then the spinel is inverted.
7 If the divalent AII is a transition metal (with configurations other
than d0 ; highspin d5 & d10) and the BIII ion is a non transition
metal, there is a tendency to form inverse spinel.
8 But there are exceptions like FeAl2O4 which has normal spinel
structure.
9 Above generalizations are valid for high spin systems as the oxide
ion is expected to be a weak field ligand.
10 For example, Co3+ is a low spin system even in presence of oxo
ligands due to high charge on the ion.
AII BIII Structure

Non transition metalor Non transition metal Spinel
d0 or d5 or d10 transition structure
metal
Non transition metal A transition metal Spinel
ord0 or d5 or d10 transition with d1 or d2 or d3 or structure
metal d4 or d6 or d7 or d8 or
d9 configurations
A transition metal Non transition metal Inverse spinel
with d1 or d2 or d3 or d4 or ortransition meta
d6 or d7 or d8 or with
d9 configurations d0 or d5 or d10
configurations
Transition metal with Transition metal with Inverse spinel
higher CFSE value lower CFSE value
Magnetism In Spinels
The spinels can be ferromagnetic or anti ferrimagnetic depending on
the structure and nature of metal ions. The unpaired spins of metal ions
69
are coupled through shared oxide ions by super exchange process. In
ferrite spinels, the spins of electrons at tetrahedral sites have one
Spinels
orientation, whereas the spins of electrons at octahedral sites have
opposite orientation. If the number of spins in these two types of sites is
equal, then that spinel will be antiferromagnetic. Otherwise, it will be
ferromagnetic.
NOTES E.g. The inverse spinels - Fe3O4, NiFe2O4 and CoFe2O4 are
ferrimagnetic. In these cases, the spins of trivalent ions are cancelled out
since half of them belong to tetrahedral sites and the other half belong to
octahedral sites. However, the spins of divalent ions are not cancelled.
Hence they show ferrimagnetism.
In case of FeCr2O4 - a normal spinel, the number of spins of high
spin Cr3+ (d3) ions is equal to the number of spins of high spin Fe 2+ (d6)
ions. Hence it is antiferromagnetic.
MgAl2O4 is diamagnetic since all the electrons in the metal ions are
paired up.
Note: Antiferro magnetic substances show weak magnetism, whereas
diamagnetic substances show no magnetism at all.
Magnetism Of Ferrite Spinels
Ferrite spinels are of technological interest because of their magnetic

ordering, which can be ferrimagnetic or antiferromagnetic depending on
the structure (normal or inverse) and the nature of the metal ions. Fe 3O4,
CoFe2O4, and NiFe2O4 are all inverse spinels and are ferrimagnets. The
latter two compounds are used in magnetic recording media and as
deflection magnets, respectively.
In order to understand the magnetism of ferrites, we need to think about
how the unpaired spins of metal ions are coupled in oxides. If an oxide
ion is shared by two metal ions, it can mediate the coupling of spins by
superexchange as shown at the right. The coupling can be
antiferromagnetic, as shown, or ferromagnetic, depending on the orbital
filling and the symmetry of the orbitals involved. The Goodenough-
Kanamori rules predict the local magnetic ordering (ferromagnetic vs.
antiferromagnetic) that results from superexchange coupling of the
electron spins of transition metal ions. For ferrites, the strongest coupling
is between ions on neighboring tetrahedral and octahedral sites, and
the ordering of spins between these two sites is
reliably antiferromagnetic.
70
Spinels
NOTES
Because all the tetrahedral and octahedral sites in a spinel or inverse

spinel crystal are coupled together identically, it works out that ions on
the tetrahedral sites will all have one orientation (e.g., spin down) and
ions on all the octahedral sites will have the opposite orientation (e.g.,
spin up). If the number of spins on the two sites is the same, then the
solid will be antiferromagnetic. However, if the number of spins is
unequal (as in the case of Fe3O4, CoFe2O4, and NiFe2O4) then the solid
will be ferrimagnetic. This is illustrated above for Fe3O4. The spins on
the Fe3+ sites cancel, because half of them are up and half are down.
However, the four unpaired electrons on the Fe2+ ions are all aligned the
same way in the crystal, so the compound is ferrimagnetic.
5.5 Perovskite Structure
Perovskites are ternary oxides of general formula ABO3. More
generally, the perovskite formula is ABX3, where the anion X can be O,
N, or halogen. The A ions are typically large ions such as Sr 2+, Ba2+,
Rb+, or a lanthanide 3+ ion, and the B ions are smaller transition metal
ions such as Ti4+, Nb5+, Ru4+, etc. The mineral after which the structure is
named has the formula CaTiO3.
The perovskite structure has simple cubic symmetry, but is related to the
fcc lattice in the sense that the A site cations and the three O atoms
comprise a fcc lattice. The B-site cations fill 1/4 of the octahedral holes
and are surrounded by six oxide anions.
71
Figure: ABX3 perovskite structure. A, B, and X are white, blue, and red,
respectively.
Spinels
The coordination of the A ions in perovskite and the arrangement
of BO6 octahedra is best understood by looking at the ReO3 structure,
which is the same structure but with the A-site cations removed. In the
polyhedral representation of the structure shown below, it can be seen
NOTES that the octahedra share all their vertices but do not share any octahedral
edges. This makes the ReO3 and perovskite structures flexible, like three-
dimensional wine racks, in that the octahedra can rotate and tilt
cooperatively. Eight such octahedra surround a large cuboctahedral
cavity, which is the site of the A ions in the perovskite structure. Cations
in these sites are coordinated by 12 oxide ions, as expected from the
relationship between the perovskite and fcc lattices.
Figure: Polyhedral representation of the ReO3 structure showing the large

cuboctahedral cavity that is surrounded by 12 oxygen atoms.
Because the A-site is empty in the ReO3 structure, compounds with that
structure can be reversibly intercalated by small ions such as Li+ or H+,
which then occupy sites in the cuboctahedral cavity. For example, smart
windows that darken in bright sunlight contain
the electrochromic material WO3, which has the ReO3 structure. WO3 is
a light yellow compound containing d0 W(VI). In contrast, HxWO3,
which is mixed-valent W(V)-W(VI) = d1-d0, has a deep blue color. Such
coloration is typical of mixed-valence transition metal complexes
because their d-electrons can be excited to delocalized conduction band
levels by red light. Because the electrochemical intercalation-
deintercalation process is powered by a solar cell, the tint of the windows
can adjust automatically to the level of sunlight.
FERROELECTRIC PEROVSKITES:
The flexibility of the network of corner-sharing BO6 octahedra is also
very important in ferroelectric oxides that have the perovskite structure.
In some perovsites with small B-site cations, such as Ti4+ and Nb5+, the
cation is too small to fit symmetrically in the BO 6 octahedron. The
octahedron distorts, allowing the cation to move off-center. These
72
distortions can be tetragonal (as in the figure shown
below), rhombohedral, or orthorhombic, depending on whether the
Spinels
cation moves towards a vertex, face, or edge of the BO 6octahedron.
Moving the cation off-center in the octahedron creates an electric dipole.
In ferroelectrics, these dipoles align in neighboring unit cells through
cooperative rotation and tilting of octahedra. The crystal thus acquires a
net electrical polarization.
NOTES
Figure: Tetragonal distortion of the perovskite unit cell in the

ferroelectric oxide PZT, PbTixZr1-xO3
Ferroelectricity behaves analogously to ferromagnetism, except that
the polarization is electrical rather than magnetic. In both cases, there is
a critical temperature (Tc)above which the spontaneous
polarization of the crystal disappears. Below T c, the electric polarization
of a ferroelectric can be switched with a coercive field, and hysteresis
loop of polarization vs. field resembles that of a ferromagnet. Above T c,
the crystal is paraelectric and has a high dielectric permittivity.
Ferroelectric and paraelectric oxides (along with piezoelectrics and

pyroelectrics) have a wide variety of applications as switches, actuators,
transducers, and dielectrics for capacitors. Ferroelectric capacitors are
important in memory devices (FRAM) and in the tuning circuits of
cellular telephones. Multiferroics, which are materials that are
simultaneously ferroelectric and ferromagnetic, are rare and are being
now intensively researched because of their potential applications in
electrically adressable magnetic memory.
Halide perovskites (ABX3, X = Cl, Br, I) can be made by combining

salts of monovalent A ions (A+ = Cs+, NH4+, RNH3+) and divalent metal
salts such as PbCl2 or PbI2. These compounds have sparked recent
interest as light absorbers for thin film solar cells that produce electricity
from sunlight. Lead and tin halide perovskites can be grown as thin films
from solution precursors or by thermal evaporation at relatively low
temperatures. In some lead halide perovskites, the mobility of electrons
and holes is very high, comparable to that of more expensive III-V
semiconductors such as GaAs, which must be grown as very pure single
73
crystals at high temperatures for use in solar cells. Because of their high
carrier mobility, some lead halide perovskites are also electroluminescent
Spinels
and are of interest as inexpensive materials for light-emitting diodes
(LEDs).
Despite their very impressive efficiency, perovskite solar cells are stable
for relatively short periods of time and are sensitive to air and moisture.
NOTES Current research is focused on understanding the degradation
mechanisms of these solar cells and improving their stability under
operating conditions.
5.6 Answer To Check Your Progress

1 The spinels are any class of minerals are general formation
AB2X4 which crystallise in the cubic crystal system, with the X
anion arranged in a cubic close-packed and the cations A and B
occupying some or all of the octahedral and tetrahedral sites in
the lattice.
2 In the normal spinel structure, there is a close-packed array of
anions.
3 Inverse spinels have a closely related structure (with the same
large unit cell) in which the A-site ions and half of the B-site ions
switch places.
4 The flexibility of the network of corner-sharing BO6 octahedra is
also very important in ferroelectric oxides that have the
perovskite structure.
5.7 Summary
 The spinels are any class of minerals are general formation

AB2X4 which crystallise in the cubic crystal system, with the
X anion arranged in a cubic close-packed and the cations A
and B occupying some or all of the octahedral and tetrahedral
sites in the lattice.
 Spinels classified can into two types. They are normal and
Inverse spinels.
 MgAl2O4 is a normal spinel since both the divalent and
trivalent ions are non transition metal ions. There is no
question of CFSE.
 Fe3O4 is an inverse spinel since the Fe(III) ion is a high spin
d5 system with zero CFSE. Whereas the divalent Fe(II) is a
high spin d6 system with more CFSE.
 The flexibility of the network of corner-sharing BO6 octahedra
is also very important in ferroelectric oxides that have the
perovskite structure.
74
5.8 Keywords
Spinels:The spinels have the general formula AB2X4. Spinels
Where: AII = a divalent cation like Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd,
Sn
BIII = a trivalent cation like Al, Ga, In, Ti, V, Cr, Mn, Fe, Fe, Co, Ni
X = O, S, Se etc.
Normal And Inverse Spinels: NOTES
In the normal spinel structure, there is a close-packed array of anions.
Inverse spinels have a closely related structure (with the same large unit
cell) in which the A-site ions and half of the B-site ions switch places.
5.9 Self Assessment And Exercise
Short Answer Questions
1 Define Spinels
2 Write the classification of the spinels
3 Give examples for Spinels
4 What are the factors affecting the structure of the spinels?
Long Answer Questions
1 Define Spinels and write the classification of the spinels?
2 What is meant byperovskites Structure?
5.10 FURTHER READING
1 Puri, Sharma and Kalia Priniciples Of Inorganic Chemistry.

Milesones Publishers and Distributors
2 Huheey, J.E., E.A. Keiter and R.L. Keiter. 2002. Inorganic
75
UNIT -6 CAGES AND CLUSTERS
Metal ions in biology
Structure
6.0 Introduction
6.1 Objectives
NOTES 6.2 Classification of metal clusters
6.3 Criteria for metal Clusters
6.4 Types of metal clusters
6.4.1 Dinuclear Clusters
6.4.2 Trinuclear Clusters
6.4.3 Tetranuclear Clusters
6.4.4 Hexanuclear Clusters
6.5 Answers to check your progress
6.6 Summary
6.7 Key words
6.9 Further Reading
6.0 Introduction
Metal-metal bond is a bond between two metal centers,
particularly between two transition metal atoms, which ranges from a
single to a quadruple bond. The existence of metal-metal bond is mainly
because of the presence of (n+1)s, (n+1)p and nd orbitals as valence shell
electronic configuration. The transition metals can form three general
types of bonds such as covalent bonds, dative bonds and weak metal-
metal symmetry interactions where covalent bonds being the strongest
and symmetry interactions are the weakest. The compounds containing a
large number of metal-metal bonds forming triangular and larger
structures are called cluster compounds, however these also include
linear M-M bonds. The metal clusters can also be defined as any entity
that contains a metal-metal bond. The journey started with the
identification of the Hg-Hg in the Hg2+ion (Hg2Cl2) which was the first
d-block metal-metal bonded species. Most of these cluster compounds
are homo-metallic, however there are few exceptions with heterometallic
cluster compounds.
6.1 Objectives
After going through this unit, you will be able to;
 To know the meaning of Cages and Clusters
 Discuss about the classification of metal Clusters
 Understand the types of metal Clusters
76
Definition of Clusters And Metal Clusters
Clusters are aggregates of 2–10n (n  6 or 7) particles (atoms or
molecules). Constituent particles may be identical or they can be two or Model Question
more different species. Clusters may be studied in the gas phase, in a paper
cluster ―molecular‖ beam, adsorbed onto a surface or trapped in an inert
matrix. Clusters are formed by most of the elements in the periodic table
– even the noble gases. Clusters of the coinage metals (copper, silver and
gold) are found in stained glass windows. Silver clusters are important in NOTES
photography. Molecular clusters are present in the atmosphere. Carbon
nanoclusters (e.g. C60 and related fullerenes) may be present in soot and
even in space.
Clusters are of fundamental interest, because
due to their intrinsic properties
because of their central position between molecular and
condensed matter science.
Clusters span a wide range of particle size – from molecular to
micro-crystalline.
Clusters constitute new materials (nano-particles) which may
have properties that are distinct from those of discrete molecules or
bulk matter.
Cluster
It is defined as ensemble of atoms or molecules intermediate in size
between a molecule and a bulk solid. The can be made up of diverse
nuclearities and stoichiometry. Examples: Fullerene, Diborane, Water
Metal Cluster: (1) Compounds that contain metal-metal bonds. (2) A
compound that contains a group of two or more atoms where direct and
substantial metal bonding is present.
Examples: Co2(CO)8, Rh2(OAc)4, Stryker‘s reagent.
6.2 Classification of Metal Clusters
Metal cluster have been classified in to two major catagories:
 The polynuclear carbonyl, nitrosyl and related clusters can be
catagorized as Class I. These clusters are mainly formed by
metals in lower oxidation states (-1, +1) which include the metal
ions residing on the right hand side of the periodic table.
 The other category (Class II) includes clusters formed as halides
and oxides of transition metal complexes in their higher oxidation
states. The transition metals lying on the left hand side of the
periodic table (second or third row transition metals) form such
type of cluster compounds. For example, the [Re2Cl8]2- cluster
contains a Re-Re single bond with +3 oxidation state on each
rhenium center in the cluster.
6.3 Criteria For Metal Cluster Formation
There is general trend that transition metals having large energies of
atomization (Zr, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Re, Os, Ir and Pt)
display higher tendancy to form metal clusters.
77
Nature of the d-orbital: The effective nuclear charge is inversely related
to the size of the d-orbital. Higher nuclear charge tends to reduce the
effective overlap of the d-orbitals which is unfavourable for cluster
formation. For example, the first row transition metals with higher
oxidation states (+2, +3) do not offer sufficient orbital overlap and
therefore poses an unfavourable situation towards cluster formation.
NOTES 6.4 Types of Metal Clusters
6.4.1 Dinuclear clusters
The first dinuclear culster studied in detail was the species [Re2X8]2-. The
structural features were studied by Prof. F. A. Cotton. Surprisingly, the
Re-Re bond distance was found to be 224 pm which is very less than the
average Re-Re distance 275 pm in Re metal. Secondly, the distance
between the chlorine atoms is nearly 330 pm which is less than the sum
of their Van der Waals radii (340-360 pm)
Cotton introduced the concept of a quadruple bond between the two

rhenium centers. The chlorine atoms are connected to the rhenium ion in
a square planar array. These are arranged in a staggered configuration
forming a square anti-prism rather than a cube. Few other examples
which involves metal-metal multiple bonded cluster are the hexa-alkoxo
dinuclear tungsten and molybdenum complexes of the formula
[M2(OR)6] where M = Mo, W.
6.4.2 Trinuclear cluster

Among all, the best studied examples of trinuclear clusters are those of
Re such as rhenium trihalides [(ReCl3)3] and their derivatives.
Self-Instructional Material Each rhenium atom is bonded with the other two rhenium atoms by a
metal-metal single bond. They are also bonded indirectly to three
78
bridging chloride atom whereas each rhenium ion is also bonded with
two chloride ions above and below Re triangular planes. The rhenium
atoms form a triangle. The Re(III) ions have a d 4 configuration. If Re Model Question
ions are bonded with Re-Re single bonds only, the complex would have paper
been a paramagnetic complex. However, the complex is diamagnetic
which implies that the Re ions are doubly bonded.
6.4.3 Tetranuclear cluster
A number of tetranuclear cluster are known in which most of them exist NOTES
as halides and oxides of tungsten and molybdenum, metals. Only a few
examples of tetranuclear clusters of halides and oxides are known. Most
important example is the dimeric [Mo 2Cl8]4- cluster giving a tetra nuclear
molecule :
6.4.4 Hexanuclear Cluster

Metal clusters containing six metal atoms have been known for many
years; mostly consist of molybdenum, niobium and tantalum atoms.
Considering the case of metal chlorides, the first type of hexanuclear
cluster consist of an octahedron of six metal atoms surrounded by eight
chloride ions one on each face of the octahedron. In this way, the
chloride ions are forming a cube around the metal octahedron. For
example, such kind of arrangement can be seen in ‗molybdenum
dichloride‘ Mo6Cl12 which can also be formulated as [Mo 6Cl8]Cl4. In this
case, each Mo(II) ion is sharing four single bonds with four other Mo(II)
ions and also receive four dative bonds from four chloride ions. In the
second type, twelve halide ions are surrounding the Mo octahedron and
placed along the edges. Such types of clusters are formed by niobium and
tantalum. Unlike the bonding situation in hexanuclear metal clusters
discussed above, each metal ion is surrounded by a distorted square
prism of four metals and four chloride ions. These compounds are
electron deficient.
COMPOUNDS WITH METAL-METAL MULTIPLE BONDS

As has been shown earlier, the earlier metals in d-block series in
their lower oxidation states have tendency to form metal-metal multiple
79
bonds. These metal-metal bonds may be present in smaller molecules and
also in macro-chain solids.
CHEVREL-PHASES
Chevrel phases generally involve tertiary molybdenum
chalcogenides, MxMoX6, polynuclear clusters, which have characteristic
properties (specially electrical and magnetic). Their structures are also
NOTES abnormal. An important example of these phases is a super-conducter
substance, PbMo6S8. Its structure consists of an octahedral cluster of
molybdenum atoms, which is surrounded by cubic cluster of sulphur
atoms. Then this whole structure is enclosed in to a cubic structure of
lead atoms. The internal Mo 6S8 cubic structure rotates with respect to
lead lattice. This rotation is due to strong repulsion between sulphur
atoms. Similarly, the superconductivity originates due to overlapping of
d-orbital of molybdenum.
 = Mo, o = s, 0 = Pb
Metal Carbonyl And Halide Clusters
As has been described earlier, metal carbonyl clusters are rarely
formed by earlier d-block metals; while that of f-metals are unknown, i.e.
these clusters are formed by group 6 to 10 elements.
An alternative method for counting skeletal electrons in these
compounds is due to D.M.P. Mingos and J. Lauher. This method is also
based on Wade's rule and is known as Wade-Mingos-Lauher rule. In this
method the total number of valence electrons in all the metal atoms
present in the complex are counted and then electrons donated by ligands
are added. Thus in Rh6(CO)16-
6Rh = 6x9 = 54 e-
16CO = 16 x 2 = 32 e-
-
Total = 86 e
-
Out of the total 86e , twelve electrons per rhodium atom are used
for non framework bonding, and remaining 14e -are obtained for skeletal
bonding. These include seven bonding paris, equal to 2n+2 electron.
Hence, Rh6(CO)16 should have closo- structure
Some examples showing inter-relation between cluster-valency
electrons and structures are given in Table
80
No. of Geometry Metal Bonding No. of Examples
Metal Skeleton Molecula Cluster
Atom Structure r Orbital electro Model Question
s n paper
1. Monomer 9 18 Ni(CO)4
2. Dimer 17 34 Fe(CO)9,
Mn2(CO)10
3. Triangle 24 48 Os3(CO)12, NOTES
Co3(CO)9CH
4. Tetrahedro 30 60 Co4(CO)12,
n Rh4(CO)12
Butterfly 31 62 Re4(CO)162-,
[Fe4(CO)12C]
2-
Square 32 64 Os4(CO)16,
Pt4(O2CMe)8
5. TBP 36 72 Os5(CO)16
Octahedral 37 74 Fe5(CO)15C
6. Trigonal 43 86 Ru6(CO)17C
prism
It is quite clear from table in tetranuclear metal cluster three structures,

tetrahedral, butterfly and square planar, are seen, with 60, 62 and 64
cluster electrons respectively.
Tetrahedron Butterfly Square Planar
81
6.5 Answer To Check Your Progress
Metal ions in biology  Metal-metal bond is a bond between two metal centers,
particularly between two transition metal atoms, which ranges from
a single to a quadruple bond.
 Metal classified into two types based on their Oxidation states.
 It is important to understand the criteria for the metal clusters.
NOTES  First Dinuclear compound found by Prof. F. A. Cotton
6.6 SUMMARY
 The transition metals can form three general typesof bonds such
as covalent bonds, dative bonds and weak metal-metal
symmetryinteractions where covalent bonds being the strongest and
symmetry interactions are theweakest
 The important criteria for the formation of metal clusters the large
energy of atomization of transistion metal and nature of the d-orbital.
 Metal clusters can be classified into four types.They are
Dinuclear metal clusters, Trinuclear metal clusters, Tetranuclear clusters
and Hexanuclear clusters.
6.7 Keywords
CAGES: It is defined as three dimensional ordered structure in solution.
CLUSTERS: A metal clusters may be defined as a group of two or more
metal atoms that are directly linked to one another through metal-
metal bonds.
6.8 Self Assessment Questions And Exercises
Short Answer Questions
1. Define Cages and Clusters
2. What is the criteria for the formation of the metal clusters?
3. What is the classification of metal clusters based on oxidation
state?
Long Answer Questions
Define Cages and classify the types of metal clusters?
6.9 Further Reading
1. Puri, Sharma And Kalia Priniciples Of Inorganic Chemistry.
Milesones Publishers And Distributors
Chemistry: Principles of Structure and Reactivity, 4th Edition. New
York: Harpercollins Publishers.
82
UNIT 7 BORANES
Structure Boranes
7.0 Introduction
7.1 Objectives
7.2.2 Classification NOTES
7.3.3 Synthesis
7.3 Carboranes
7.3.1 Nomenclature
7.3.2 Preparation
7.4 Wade‘s rules
7.5 STYX notation
7.5.2 4n rules
7.5.3 5n rules
7.5.4 6n rules
7.8 Summary
7.9 Keywords
7.0 Introduction
Boranes is the name given to the class of synthetic
hydrides of boron with a general formula of BxHy. Lipscomb was
awarded the Nobel prize in Chemistry in 1976 for his achievements in
this field.Polyhedral skeletal electron pair theory (Wade's rules) can be
used to predict the structures of boranes. In this unit, we are going in
detail about the structural classification of boranes, bonding in polyhedral
boranes, LIPCOMB‘s styx rule and Wades rule. Further, we are also
going to discuss carborances, borazines and isolable analogy with
suitable examples.
7.1 Objectives
The main aim of this unit is to study the nature, methods of
preparation and structures of metal-clusters. After going through this unit
you should be able to:
 describe boranes and higher boranes with reference to their
classification, synthesis reactions and structures;
 discuss carboranes and explain their synthesis and properties in
the light of their structures;
 identify compounds with metal-metal multiple bonds and their
structures.
83
 Learn about the Lipcomb‘s STYX codes.
 Understand the concepts behind bonding in polyhedral borances.
Boranes
 Explain aboutWade‘s rule.
 Explain about carborances
 Learn about the Isolabal Analogy.
NOTES Boron hydrides are known as Boranes. These are named boranes
in analogy with alkanes. These are gaseous substance at ordinary
temperatures. Boranes is the name given to the class of synthetic
hydrides of boron with generic formula BxHy. In the past, borane
molecules were often labeled " electron-deficient" because of their
multicenter bonding (in which a pair of bonding electrons links more
than two atoms, as in 3-center-2-electron bonds); this was done in order
to distinguish such molecules from hydrocarbons and other classically
bonded compounds.
A) The latin prefixes mono, di, tri, etc are used before ―BORANCES‖ to
indicate the number if boron atoms in the compound.
B) Immediately following the ‗e‘ in ‗borane‘ the number of hydrogen
atoms is placed in parentheses using Arabic numerals.
Examples; B5H11 is pentaborane (11)
C) Whereas the names of anions end in ―ate‖ rather ―ane‖.The numbers
of both borane and hydrogens are indicated by latin prefixes.
Examples: B10H102-is decahydrodecarborate (2- )
It is expected that boron would form the hydride BH3, but this
compound is unstable at the room temperature. However, higher hydrides
like B2H6(diborance). B4H12 (tetraborane), B6H10(hexaborane),
B10H14(decaborane) etc. are known. The general formula of boranes are
BnHn + 4 and BnHn + 6. In addition to these is one, recently discovered
series of closed polyhedral structures with the formula [BnHn] 2-. Higher
boranes have different shapes, some resemble with nests, some with
butterfly and some with spider's web.
The modern explanation of the structure of boranes is due to

C.L.Higgins, who proposed the concept of three centred two electron
bond (  -bond). He also proposed the concept of completely delocalised
molecular orbitals to explain structures of boron polyhedrons.
84
In higher boranes, in addition to two centred two electron (2c, 2e) and the
three centred two electron bond (3c, 2e bond) present in diborance, B-B
2C, 2e and B-B-B (3c, 2e) bonds are also important. In B-B-B bonds, Boranes
three atoms of boron with their sp3 hybridisation are placed at the
corners of a equilateral triangle.
The structures of boranes can be classified according to the following NOTES
scheme:
 closo boranes have the formula BnHn2-(n vertices of cornered
polyhedron are occupied by boron atoms)
 nido boranes are formally derived from BnHn4-ions (1 vertex is
missing from parent closo borane)
 arachno boranes are formally derived from B nHn6- ions(2 vertex
is missing from parent closo borane)
 hypho boranes are formally derived from BnHn8- ions(3 vertex is
 klado boranes are formally derived from BnHn10- ions(4 vertex is
Name Formula Skeletal Examples

Electron
Pair
Closo [BnHn]2- n+1 [B5H5]2- to [B12H12]2-
Nido [BnHn+4] n+2 B2H6 , B5H9, B6H19
Arachno [BnHn+6] n+3 B4H10 , B5H11
Hypo [BnHn+8] n+4 Only derivatives are known.
Closo Boranes
These are closed structured (Closo, Greak, meaning cage) boranes with
the molecular formula [BnHn]2- and skeletal electrons = n+1 pairs (=
2n+2 electrons). In this structure, there is one boron atom placed at each
apex and there are no B-H-B bonds present in the molecule. All the
member of the series from n=5 to 12 are known. [B5H5]2- is trigonal
bipyramidal, [B6H6]2- is octahedral and [B12H12]2- is icosahedral. All are
stable on heating and are quite inert.
Nido-Boranes
These boranes have nest (Nido, Latin, meaning Nest) like structure.
Their general formula is BnHn+4 and have (n+2) pairs = 2n+4 skeletal
electrons on removing one boron atom from an apex of closo structure,
nido structure is obtained. Because, of the lost boron atom, these
boranes have extra hydrogens for completing the valency. The
polyhedra in this series have B-H-B bridge bonds in addition to B-B
bonds. They are comparatively less stable than 'Closo', but more than
'Arachno' on heating.
Arachno-Boranes
85
These boranes have the general formula (BnHn+6) and skeletal electrons
of (n+3) pairs = 2n+6 = electrons. These molecules are obtained by
Boranes
removing two boron atoms from two apexes of the closo structure and
have spider-web like structure. They have B-H-B bridge-bonds in their
structures and are very reactive and unstable on heating.
Structural Inter-relation
H
B
H
NOTES H B
B
H H H
HB +4H -2e - H
BH B H +2H B H
B BH B H
-BH H B H
-BH B
B B
H H H
H H H
B
H H H
Closo structure Nido structure

[B6H6]2- Archano structure
[B5H9]
[B4H10]
This is based on the observation that the structures having same number
of skeletal electrons are related with one another by the removal of BH
unit one by one and the addition of suitable number of electrons and
hydrogen atoms.
7.2.3 Synthesis
The simplest method for synthesis of higher boranes is the controlled
pyrolysis of diborance, B2H6 it is a gas phase reaction, BH3 formed in the
first step reacts with borane to give higher boranes
B2H6(g) 2BH3(g)
B2H6(g)+ BH3(g) B3H7(g)+ H2(g)
B3H7(g)+ BH3(g) B4H10(g)
B2H6(g)+ BH3(g) B3H9(g) [B3H8]-(g)+ H+
5[B3H6(g) [B12H12]2-(g) + 3[BH4]-(g) + 8H2(g)
2[BH4]-(g)+5B2H6(g) [B12H12]2-(g) + 13H2(g)
Reactions
The important reactions of higher boranes are with Lewis bases, which
involve removal of BH2 or BHn from the cluster, growth of the cluster or
removal of one or more number of protons:
1. Decomposition by Lewis-bases:
B4H10 + 2NH3 [BH2(NH3)2] + [B3H8]
86
The reaction is analogous to the reaction of diborane with ammonia.
2. Deprotonation :
Higher boranes give deprotonation reaction easily rather than Boranes
decomposition:
B4H10 + N(CH3)3 [HN(NH3)3] + [B10H13] -
This deprotonation takes place from 3c, 2e BHB-bond. The bronsted
acidity of boranes increases with their size:
NOTES
B4H10< B5H9< B10H14
For deprotonation of B5H9 strong-base like Li4(CH3)4 is required:
B5H9 + Li(CH3) Li+[B5H8]- + CH4
4. Electrophilic displacement of proton:
Electrophilic displacement of proton by the catalytic activity of Lewis
acids like AlCl3 is the basis of alkylation and halogenation of boranes:
AlCl3
B5H9 + CH3Cl [CH3B5H8] + HCl
7.3 Carboranes
Carborane, any member of a class of organometallic compounds
containing carbon (C), boron (B), and hydrogen(H). The general formula
of carboranes is represented by C2BnHn + 2, in which n is an integer;
carboranes with n ranging from 3 to 10 have been characterized. The first
carboranes were produced in the 1950s, but the results were not
declassified and published until 1962–63. Since then, many thousands of
carboranes have been prepared, and they have been combined with
transition metals to yield derivatives called metallacarboranes, some of
which show catalytic activity. Carboranes are electron-delocalized (non-
classically bonded) clusters composed of boron, carbon and hydrogen
atoms that may also contain other metallic and nonmetallic elements in
the cluster framework. Like many of the related boron hydrides, these
clusters are polyhedra or fragments of polyhedra, and are similarly
classified as closo-, nido-, arachno-, hypho-, etc. based on whether they
represent a complete (closo-) polyhedron, or a polyhedron that is missing
one (nido-), two (arachno-)three (hypho-), or more vertices. Carboranes
are a notable example of heteroboranes.
87
The utility of carboranes as pharmacophores in drug design (molecules
that facilitate recognition and binding by biological macromolecules)
Boranes
motivates medicinal applications. Unlike boranes, which are generally
quite moisture sensitive, some carboranes are kinetically stable to
hydrolysis, permitting their usein vivo. Carboranes may be classified by
structural type using the same method described previously for boranes.
NOTES Because a carbon atom has the same number of valence electrons
Type Borane Example Carborane Example

2- 2-
closo BnHn B12H12 C2Bn-2Hn C2B10H12
nido BnHn+4 B10H14 C2Bn-2Hn+2 C2B8H12
arachno BnHn+6 B9H15 C2Bn-2Hn+4 C2B7H13
Examples of Formulas of Boranes and Carboranes
as a boron atom plus a hydrogen atom, formally each C should be
converted to BH in the classification scheme. For example, for
acarborane having the formula C2B8H10,
C2B8H10 B10H12
B10H12 + 2 H+ = B10H102-
the classification of the carboranes C2B8H10 is therefore closo.
Closo-Carboranes: These have closed cage structrues in which

hydrogen bridges are structurally analogous to the BnHn-2 anions with B-
replaced by isoelectronic carbon. These carboranes have the general
formula. C2Bn+2 (n=3) to 12. The important member is C2B10H12 which is
isoelectronic with [B12H12]2- similarly B4C2H6 is isoelectronic with
[B6H6]2-.
Nido Carboranes: They are having an open case structure in which

some framework members are attached likely by hydrogen bridges.
These are derived formally from one or other of several borones.
These contain one to four carbon atoms in the skeleton.
In addition to the above types of carboranes, there are a number of

carboranes with an additional heteroatom such as phosphorus built into
the basic structure and a family of metallo carboranes, some of which are
similar to ferrocene. One peculiar feature common to all carboranes is
that to date no compound hasbeen synthesized with either carbon
bridging two boron atoms in a three centre two electron bond or acting as
one end off a hydride bridge.
First carborane was obtained in 1953 when mixtures of diborane and

acetylene were ignited with a hot wire. Since that time, many new
carboranes have been isolated.
88
7.3.1 Nomenclature
Rules for naming carboranes are as follows:
i. First of all, give the positions and number of carbon atoms, then the Boranes
type of carborane (either closo or nido) and finally the name of the
borane from which the carborane is formally derived and the number of
hydrogen atoms shown in bracket. For example CB5H9 is name as
monocarbonido hexaborane (9). Similarly, the three isomers of NOTES
C2B10H12 are named as 1, 2; 1, 7 and 1, 12 dicarbo-closo-dodecaborane
(12).
ii. Number of atoms in these structure are counted by starting the
numbering from that in the apical position and proceeding through
successive rings in a clockwise direction.
This rule is important in naming the isomers.
Closo-Carboranes or Closed Cage Carboranes
These carboranes are having general formula C2 BnHn+2 (n=3 to 10) in
which the constituents are only terminal. These are isoelectronic with the
corresponding [BnHn]2- ions and have the same closed polyhedral
structures, with one hydrogen atom bonded to each carbon and boron. No
bridging hydrogen atoms are present in the C2Bn skeleton. They are
considered in three groups.
a. small, n = 3 - 5
b. large, n = 6-10 and
c. dicarbo-closo-dodecaborone
7.3.2 Preparation
(a) The Small Closo Carboranes (C2BnHn+2 where n = 3 to 5)
B5H9 + C2H2 1,5 - C2B3H5 + 1,6 - C2B4H6 +2,4 - C2B5H7
Example - The closo hexaborane isomers, C2BnH6,
(b) The Large Closo Carboranes (C2B2Hn+2 where n = 6 to 9)
The first three members of this group of carboranes are obtained by the
thermolysis of 1,3 - C2B7H13 and 1,3 - C2B2H12.
Example :C2B6H8 is made from hexaborane (10) and dimethylacetylene.

The structure of 1,7 - Me2C2B6H6 is based on the bicapped triangular
prism. The carbon atoms are present one on the prism and the other
above the face opposite.
(c) Dicarobo-closo-dodecaborone:
Preparation: The orthocarborane is the only isomer which can be
synthesized directly. However, it is synthesized by the base catalysed
reaction of acetylenes with decarborane (14) or via B10H12L2.
B10H14 + 2L  B10H12L2 + R2C2R2L2B10H10 + H2 + 2L
Example: C2B10H12 gives three isomeric structure - 1,2 (ortho), 1-7
(meta) and 1, 12 (para)
Nido-Carboranes or Open Cage Carboranes

These structures are derived formally from one or other of several
boranes and contain from one to four carbon atoms in the skeleton.
89
Examples: CB5H9, C2B4H8, C3B3H7, C4B2H6 etc.
Preparation: The smaller nido-carboranes are generally prepared by
Boranes
reacting a borane with acetylene under mild conditions.
Example: B5H9 and C2H2 undergo reaction in the gas phase at 215°C to
give mainly the nidocarborane 2,3 - C2B4H8 together with methyl
derivatives of CB5H9.
NOTES The preparation method described above does not yield a single product
but a mixture of several products whose separation is not an easy task.
However some smaller nidocaroranes are prepared by the following
specific methods:
i. Mono carbo-nido-hexaborane (7) CB5H7 is formed by passing silent
electric discharge through 1-methyl pentaborane (9).
ii. The only example isoelectronic with B5H9 is 1,2- dicarbonido -
pentaborane(7), C2B3H7, which is prepared as follows:
B4H10 + C2H2 C2B3H7 (3 - 4 % yield)
iii. Monocarbonidohexaborane (9), CB5H9 is formed from
ethyldifluoroborane and lithium.
The nido-carboranes are formally related to B6H10. All are having eight
pairs of electrons which are bonding the six cage atoms together.
Large Nido-Carborane:
Dicarbo-nido-undecaborane, C2B9H13, is the second member of the class
of nido-carboranes C2BnHn+4 (n =4 or 9), The parent carborane and its
substituted derivatives can be prepared by the base degradation of ortho-
carborane (1,2-dicarbocloso-dodecaborane (C2B10H12).
1,2 - C2H10H12 + MeO- C2B9H12 C2B9H13
When C2B9H13 is heated, the closo-undeca-Borone (11) cage is formed.
7.3.3 Properties
Properties of carboranes resemble with that of the corresponding boranes
closely. Thus, 1.2 dicarbo closo-dodecarborane-12 is stable in both air
and heat. On heating in inert atmosphere at 500 °C, it is converted into 1,
7 isomer i.e. meta or neo isomer; while at 700 °C it is concerted to 1, 12
isomer i.e. para-isomer.
7.4 Wade’s rules
Ken Wade developed a method for the prediction of shapes of borane
clusters; however, it may be used for a wide range of substituted boranes
(such as carboranes) as well as other classes of cluster compounds.
Wade‘s rules are used to rationalize the shape of borane clusters by
calculating the total number of skeletal electron pairs (SEP) available for
cluster bonding. In using Wade‘s rules it is key to understand structural
relationship of various boranes.
The general methodology to be followed when applying Wade‘s rules is

as follows:
90
1. Determine the total number of valence electrons from the
chemical formula, i.e., 3 electrons per B, and 1 electron per H.
2. Subtract 2 electrons for each B-H unit (or C-H in a carborane). Boranes
3. Divide the number of remaining electrons by 2 to get the number
of skeletal electron pairs (SEP).
4. A cluster with n vertices (i.e., n boron atoms) and n+1 SEP for
bonding has a closo structure.
NOTES
5. A cluster with n-1 vertices (i.e., n-1 boron atoms) and n+1 SEP
for bonding has a nido structure.
for bonding has an arachno structure.
for bonding has anhypho structure.
8. If the number of boron atoms (i.e., n) is larger than n+1 SEP then
the extra boron occupies a capping position on a triangular phase.
What is the structure of B5H11?
1. Total number of valence electrons = (5 x B) + (11 x H) = (5 x 3)

+ (11 x 1) = 26
2. Number of electrons for each B-H unit = (5 x 2) = 10
3. Number of skeletal electrons = 26 – 10 = 16
4. Number SEP = 16/2 = 8
5. If n+1 = 8 then n = 7and n-2 = 5 boron atoms,
6. Structure of n = 7 is pentagonal bipyramid, therefore B5H11 is an
arachno based upon a pentagonal bipyramid with two apexes
missing.
What is the structure of B6H62-?
1. Total number of valence electrons = (6 x B) + (3 x H) = (6 x 3) +

(6 x 1) + 2 = 26
2. Number of electrons for each B-H unit = (6 x 2) = 12
3. Number of skeletal electrons = 26 – 12 = 14
4. Number SEP = 14/2 = 7
5. If n+1 = 7 and n boron atoms, then n = 6
6. Structure of n = 6 is octahedral, therefore B6H62- is a closo
structure based upon an octahedral structure.
7.5 STYX notation
The description of the bonding in the larger boranes formulated by
William Lipscombwhich accounts for
 3-center 2-electron B-H-B hydrogen bridges

 3-center 2-electron B-B-B bonds
 2-center 2-electron bonds (in B-B, B-H and BH2)
91
The styx number was introduced to aid in electron counting. Lipscomb's
methodology has largely been superseded by a molecular orbital
Boranes
approach, although it still affords insights. The results of this have been
summarized in a simple but powerful rule, PSEPT (Polyhedral Skeletal
Electron Pair Theory), often known as Wade's rules, that can be used to
predict the cluster type, closo-, nido-, etc. The power of this rule is its
NOTES ease of use and general applicability to many different cluster types other
than boranes.
where
s = count of 3-center B-H-B bonds;
t = count of 3-center B-B-B bonds;
y = count of 2-center B-B bonds and
x = count of BH2 groups.
The polyhedral skeletal electron pair theory (PSEPT) provides electron
counting rules useful for predicting the structures of clusters such as
borane and carborane clusters. The electron counting rules were
originally formulated by kenneth wade and were further developed by
michael mingos and others; they are sometimes known as wade's rules or
the wade–mingos rules. the rules are based on a molecular orbital
treatment of the bonding. these rules have been extended and unified in
the form of the jemmis mno rules.
Different rules (4n, 5n, or 6n) are invoked depending on the number of
electrons per vertex.
The 4n rules are reasonably accurate in predicting the structures of
clusters having about 4 electrons per vertex, as is the case for many
boranes and carboranes. For such clusters, the structures are based on
deltahedra, which are polyhedra in which every face is triangular. The 4n
clusters are classified as closo-, nido-, arachno- or hypho-, based on
whether they represent a complete (closo-) deltahedron, or a deltahedron
that is missing one (nido-), two (arachno-) or three (hypho-) vertices.
However, hypho clusters are relatively uncommon due to the fact that the
electron count is high enough to start to fill antibonding orbitals and
destabilize the 4n structure. If the electron count is close to 5 electrons
per vertex, the structure often changes to one governed by the 5n rules,
which are based on 3-connected polyhedra.
As the electron count increases further, the structures of clusters with 5n

electron counts become unstable, so the 6n rules can be implemented.
The 6n clusters have structures that are based on rings.
A molecular orbital treatment can be used to rationalize the bonding of

cluster compounds of the 4n, 5n, and 6n types.
92
7.5.2 4n rules
The following polyhedra are closo polyhedra, and are the basis for the 4n
rules; each of these have triangular faces. The number of vertices in the Boranes
cluster determines what polyhedron the structure is based on.
Number of vertices Polyhedron

4 Tetrahedron NOTES
5 Trigonal bipyramid
6 Octahedron
7 Pentagonal bipyramid
8 D2d (trigonal) dodecahedron (snub disphenoid)
9 Tricapped trigonal prism
10 Bicapped square antiprism
11 Edge-contracted icosahedron (octadecahedron)
12 Icosahedron (bicapped pentagonal antiprism)
using the electron count, the predicted structure can be found. n is the
number of vertices in the cluster. The 4n rules are enumerated in the
following table.
Electron Name Predicted structure

count
4n − 2 Bicapped n − 2 vertex closo polyhedron with 2 capped
closo (augmented) faces
4n Capped n − 1 vertex closo polyhedron with 1 face
closo capped
4n + 2 closo closo polyhedron with n vertices
4n + 4 nido n + 1 vertex closo polyhedron with 1 missing
vertex
4n + 6 arachno n + 2 vertex closo polyhedron with 2 missing
vertices
4n + 8 hypho n + 3 vertex closo polyhedron with 3 missing
vertices
4n + 10 klado n + 4 vertex closo polyhedron with 4 missing
vertices
When counting electrons for each cluster, the number of valence

electrons is enumerated. For each transition metal present, 10 electrons
are subtracted from the total electron count
Example:
B5H54−
93
Electron count: 5 × B + 5 × H + 4 (for the negative charge) = 5 × 3 + 5 ×
1 + 4 = 24
Boranes
Since n = 5, 4n + 4 = 24, so the cluster is nido.
Starting from an octahedron, one of the vertices is removed.

NOTES
The rules are useful in also predicting the structure of carboranes.
Example: C2B7H13
Electron count = 2 × C + 7 × B + 13 × H = 2 × 4 + 3 × 7 + 13 × 1 = 42
Since n in this case is 9, 4n + 6 = 42, the cluster is arachno.

7.5.3 5n rules
As more electrons are added per vertex, the number of the electrons per
vertex approaches 5. Rather than adopting structures based on deltahedra,
the 5n-type clusters have structures based on a different series of
polyhedra known as the 3-connected polyhedra, in which each vertex is
connected to 3 other vertices. The 3-connected polyhedra are the duals of
the deltahedra.
Number of Type of 3-connected polyhedron
vertices
4 Tetrahedron
6 Trigonal prism
8 Cube
10 Pentagonal prism
12 D2d pseudo-octahedron (dual of snub disphenoid)
14 Dual of triaugmented triangular prism
(K5associahedron)
16 Square truncated trapezohedron
18 Dual of edge-contracted icosahedron
20 Dodecahedron
The 5n rules are as follows.
Total electron Predicted structure

count
5n n-vertex 3-connected polyhedron
5n + 1 n – 1 vertex 3-connected polyhedron with one vertex
inserted into an edge
5n + 2 n – 2 vertex 3-connected polyhedron with two
vertices inserted into edges
5n + k n − k vertex 3-connected polyhedron with k vertices
inserted into edges
94
7.5.4 6n rules
As more electrons are added to a 5n cluster, the number of electrons per
vertex approaches 6. Instead of adopting structures based on 4n or 5n Boranes
rules, the clusters tend to have structures governed by the 6n rules, which
are based on rings. The rules for the 6n structures are as follows.
Total electron Predicted structure NOTES

count
6n – k n-membered ring with k⁄2 transannular bonds
6n – 4 n-membered ring with 2 transannular bonds
6n – 2 n-membered ring with 1 transannular bond
6n n-membered ring
6n + 2 n-membered chain (n-membered ring with 1
broken bond)

Provided a vertex unit is isolobal with BH then it can, in principle at
least, be substituted for a BH unit, even though BH and CH are not
isoelectronic. The CH+ unit is isolobal, hence the rules are applicable to
carboranes. This can be explained due to a frontier orbital treatment.
Additionally there are isolobal transition-metal units.

An important contribution to the understanding of parallels
between organic and inorganic chemistry has been the concept of
isolobal molecular fragments, described elaborately by Roald Hoffmann
in his 1981 Nobel lecture. Hoffmann defined molecular fragments to be
isolobal if the number, symmetry properties, approximate energy and
shape of the frontier orbitals and the number of electrons in them are
similarnot identical, but similar.
The fragments can be combined into molecules; two CH 3
fragments form ethane, and two Mn(CO)5 fragments form (OC)5Mn-
Mn(CO)5. Furthermore, these organic and organometallic fragments can
be combined to afford H3C-Mn(CO)5.
The organic and organometallic parallels are not always this
complete. For example, although two 6-electron CH2 fragments form
ethylene, H2C=CH2, the neutral dimer of the isolobalFe(CO)4 is known
only as a transient species, obtained photochemically from Fe 2(CO)9.
However, both CH2 and Fe(CO)4 form three-membered rings,
cyclopropane and Fe3(CO)12. Although cyclopropane is a trimer of
three CH2 fragments, Fe3(CO)12 has two bridging carbonyls and is
therefore not a perfect trimer of Fe(CO) 4. The isoelectronicOs3(CO)12, on
the other hand, is a trimeric combination of three Os(CO) 4 fragments,
which are isolobal with both Fe(CO)4 and CH2, and can correctly be
described as [Os(CO)4]3.
95
The isolobal species Ir(CO)3, Co(CO)3, CR (R = H, alkyl, aryl),
Boranes
and P may also be combined in several different ways. The Ir(CO) 3, a 15-
electron fragment, forms[Ir(CO)3]4, which has Td symmetry. The
isoelectronic complex Co 4(CO)12 has a nearly tetrahedral array of cobalt
atoms but has three bridging carbonyls and hence C3v symmetry.
NOTES Compounds are also known that have a central tetrahedral structure, with
one or more Co(CO)3 fragments replaced by the isolobal CR fragment.
This is similar to the replacement of phosphorus atoms in the P 4
tetrahedron by Co(CO)3 fragments; P is isolobal with CR.
Bonding in cluster compounds

B2H6:
The bonding in diborane is best described by treating each B as
sp3-hybridized. Two sp3-hybrid orbitals on each boron form the bonds to
the terminal hydrogens. The remaining sp3-orbitals create the bonds with
the bridging hydrogens. Because the angles in the diborane structure are
not tetrahedral the orbitals also likely contain some sp 2 character.
closo-B6H62−
MO diagram of B6H62− showing the orbitals responsible for
forming the cluster. The boron atoms lie on each vertex of the octahedron
and are sp hybridized. One sp-hybrid radiates away from the structure
forming the bond with the hydrogen atom. The other sp-hybrid radiates
into the center of the structure forming a large bonding molecular orbital
at the center of the cluster. The remaining two unhybridized orbitals lie
along the tangent of the sphere like structure creating more bonding and
antibonding orbitals between the boron vertices. The orbital diagram
breaks down as follows: The 18 framework molecular orbitals, (MOs),
derived from the 18 boron atomic orbitals are:
 One bonding MO at the center of the cluster and 5 antibonding MOs
from the 6 sp-radial hybrid orbitals
 6 bonding MOs and 6 antibonding MOs from the 12 tangential p-
orbitals.
The total skeletal bonding orbitals is therefore 7, i.e. n + 1.
7.6 Check your progress
1.Give the classification of boranes.
2. Classify the following boranes by structural type:a. B11H132-b. B5H8-c.
B7H72-
3. What are the STYX number?
1. Boranes fall into five structure categories:
closo (BnHn2-), nido (BnHn+4), arachno (BnHn+6), hypho (BnHn+8),
klado(BnHn10-).
2. a. B11H132- is derived from B11H114-, a nido species.
b. B5H8-is derived from B5H54-, a nido species.
c. B7H72-is a closo species.
96
3. The styx number was introduced to aid in electron counting where
s = count of 3-center B-H-B bonds;
t = count of 3-center B-B-B bonds; Boranes
y = count of 2-center B-B bonds and
x = count of BH2 groups.
7.8 Summary
 Boranes is the name given to the class of synthetic hydrides of NOTES
boron with generic formula B xHy. In the past, borane molecules
were often labeled " electron-deficient" because of their
multicenter bonding (in which a pair of bonding electrons links
more than two atoms, as in 3-center-2-electron bonds); this was
done in order to distinguish such molecules from hydrocarbons
and other classically bonded compounds.
 Boranes fall into five structure categories: closo (BnHn2-), nido
(BnHn+4), arachno (BnHn+6), hypho (BnHn+8), klado(BnHn10-).
 The styx number was introduced to aid in electron counting
where s = count of 3-center B-H-B bonds; t = count of 3-center
B-B-B bonds;y = count of 2-center B-B bonds andx = count of
BH2 groups.
 Wades rule states that clusters having ns k eletalatoms (vertices)
will adopt closo structures if it is held together by (n+1) skeletal
bonding electron pairs ; nido if held together by (n+2) skeletal
electron pairs, arachno if held together by (n+3) skeletal electron
pairs, hypho if held together by (n+4) skeletal electron pairs and
klado if held together by (n+5) skeletal electron pairs.
 Two molecular fragments are isolable if the number, symmetry
properties and shapes and approximate energies of their frontier
orbitals are the same. They may or may not be isoelectronic.
7.9 Keywords
Boranes - The name given to the class of synthetic hydrides of boron
with generic formula BxHy.
Carboranes- Any member of a class of organometallic compounds
containing carbon(C), boron (B), and hydrogen (H). The general formula
of carboranes is represented by C2BnHn+2, in which n is an integer.
Wade’s rule - used to rationalize the shape of borane clusters by
calculating the total number of skeletal electron pairs (SEP) available for
cluster bonding. In using Wade's rules it is key to understand structural
relationship of various boranes.
Borazine- A non-polar inorganic compound with the chemical formula
B3H6N3. It is isostructural and isoelectronic with benzene, and hence it is
referred as inorganic benzene.
1. Explain Lipcomb‘s Styx rule with example.
2. Give the detailed picture of the classification of boranes with
examples.
3. Give a detailed picture of carborances.
97
4. Classify the following carboranes by structural type:
a. C3B3H7 b. C2B5H7 c. C2B7H12-
Boranes
5. Explain Wade‘s rule with a suitable example.
6. Explain the preparation and properties of borazine.
7. Explain in detail about Isolable analogy suitable examples.
NOTES 1 Cotton, F.A. and G. Wilkinson. 1988. Advanced Inorganic
Chemistry, 5th Edition. New Jersey: Wiley Eastern.
2 Huheey, J.E., E.A. Keiter and R.L. Keiter. 2002. Inorganic
3 Gary L. Miessler., Paul J. Fischer., Donald A. Tarr. Inorganic
Chemistry, 5th edition : Pearson
4 Shriver and Atkins., Inorganic Chemistry, 5th ed : W. H. Freeman
98
BLOCK-3 ORGANOMETALLIC CHEMISTRY
UNIT-8 DEFINITION OF ORGANOMETALLICS Organometallic Chemistry
Structure
8.0 Introduction
8.1 Objectives
8.2.1 Reactions of Metal alkyls NOTES

8.6 Metal – Arene Complexs
8.9 Summary
8.10 Keywords
8.0 Introduction
Organometallic chemistry is the study of chemical compounds
containing at least one chemical bond between a carbon atom of an
organic molecule and a metal, including alkaline, alkaline earth, and
transition metals, and sometimes broadened to include metalloids like
boron, silicon, and tin, as well. Aside from bonds to organyl fragments or
molecules, bonds to 'inorganic' carbon, like carbon monoxide (metal
carbonyls), cyanide, or carbide, are generally considered to be
organometallic as well. Some related compounds such as transition metal
hydrides and metal phosphine complexes are often included in
discussions of organometallic compounds, though strictly speaking, they
are not necessarily organometallic. The related but distinct term
"metalorganic compound" refers to metal-containing compounds lacking
direct metal-carbon bonds but which contain organic ligands. Metal β-
diketonates, alkoxides, dialkylamides, and metal phosphine complexes
are representative members of this class. The field of organometallic
chemistry combines aspects of traditional inorganic and organic
chemistry.
Organometallic compounds are widely used both stoichiometrically in
research and industrial chemical reactions, as well as in the role of
catalysts to increase the rates of such reactions (e.g., as in uses of
homogeneous catalysis), where target molecules include polymers,
pharmaceuticals, and many other types of practical products.
Compounds that contain a metal-carbon bond, R-M, are known as
"organometallic" compounds. Organometallic compounds of Li, Mg
(Grignard reagents) are amongst some of the most important organic
reagents. Many other metals have been utilised, for example Na, Cu and
99
Zn. Organometallic compounds provide a source of nucleophilic
carbon atoms which can react with electrophilic carbon to form a new
Organometallic Chemistry
carbon-carbon bond. This is very important for the synthesis of complex
molecules from simple starting materials. To rationalise the general
reactivity of organometallics it is convenient to view them as ionic, so
R-M = R-M+
NOTES The most important reactions is this chapter are the reactions of
organolithiums, RLi, and Grignard reagents, RMgX, with the carbonyl
groups in aldehydes, ketones and esters to give alcohols. However, we
will also look at some useful reactions involving Cu, Zn and Hg
(mercury). Transition metal alkyl complexes play a critical role in a
variety of important organometallic reactions such as olefin
polymerization and hydroformylation. Early attempts to synthesize these
complexes were unsuccessful, so it was originally thought that such
species were inherently unstable due to weak metal-carbon bonds. In
fact, the issue is not their thermodynamic stability (M-C bond
dissociation energies are typically 40-60 kcal/mol with 20-70 kcal/mol
being a practical range), but their kinetic stability.
Hapticity
The term hapticity is used to describe how a group of contiguous atoms
of a ligand are coordinated to a central atom. Hapticity of a ligand is
indicated by the Greek character 'eta', η.
ηn: n = the number of contiguous atoms of the ligand that are bound to
the metal. The term is usually employed to describe ligands containing
extended -systems or where agostic bonding is not obvious from the
formula.
Example
1. Ferrocene: bis(η5-cyclopentadienyl)iron
2. Zeise‘s salt: K[PtCl3(η2-C2H4)].H2O
Uranocene: bis(η8-1,3,5,7-cyclooctatetraene)uranium
Structure and Bonding

Simple alkyls are simple sigma donors, that can be considered to donate
one or two electrons to the metal center depending on which electron
counting formalism.
For simple metal alkyls, the M-R bond distance is typically 190 to 220
pm. This is approximately the sum of the covalent radii of carbon and
metal, rC = 77 pm and r M ~120 pm. Realize that the first row transition
metals are smaller, so any M-X bond distance will usually be smaller by
10-20 pm or so.
Alkyls can bridge two metal centers, something that is well known from
aluminum-alkyl chemistry. For Al2Me6, Bridging alkyls are also known
100
for other metals such as lanthanum and zirconium. Another type of
unusual alkyl group involves agostic interactions in which part of the
alkyl substituent coordinates to the metal in addition to the M-C bond. Organometallic Chemistry
8.1 Objectives
 Understand about the stability of Metal carbon bond
 Understand the methods of synthesis of metal alkyl, alkene, arene NOTES
complexes
 Explain the concept and structure of metal alkene complexes
1. Metathetical exchange using a carbon nucleophile (R -). Much of
this alkylation chemistry can be understood with Pearson's "hard-soft"
principles. Here are just a few examples of nucleophilic routes; notice
that some of the homoleptic alkyls are rather unstable. This is because
they have low d-counts, are susceptible to alpha- and/or beta-hydride
elimination, and lack good pi-donating ligands to stabilize their high
oxidation states:
soft hard soft hard
Cp
Fe Cl + RMgX Cp(CO)2Fe-R + MgX2

OC
OC
Beware of reactions where the hard-soft interactions are not so clear as
these can represent equilibria instead of complete reactions
2) Metal alkyl complexes are prepared by taking advantage of
the nucleophilicity of a carbonylate ion.
[Mn(CO)5]- + MeI  Me Mn (CO)5 + I -
3) Interaction of sodium salts of anions with alkyl or aryl
halides.
cpW (CO)3- Na+ + CH3I  cpW (CO)3 Me + NaI
4) Oxidative – Addition reactions: This requires a covalently
unsaturated, low-valent complex (16 e- or less). A classic
example:
IrCl (CO) (PPh3)2 + CH3I Ir(CH)3(Cl)(I)(CO)(PPh3)2
5) Metal atom reactions
Ni + C6F5Br + C6H5Me NiBr2 + (C6H5)2Ni ( - C6H5 Me)
6) Metal-centered nucleophiles (i.e. using R+ as a reagent): Typical
examples are a metal anion and alkyl halide (or pseudohalogen). for
example:
NaFp + RX Fp-R + NaX [Fp = Cp(CO)2Fe]
2
SN (associative mechanism) for this reaction, but a single
electron transfer mechanism (SET) could also be postulated.
101
7) Insertion reactions:To form an alkyl, this usually involves an
olefin insertion. The simplest generic example is the insertion of
ethylene into an M-X bond, i.e.
M-X + CH2CH2 M-CH2CH2-X
8) Deinsertion. This is not a highly common method. The reaction
usually involves desinsertion of carbon monoxide from an
NOTES intermediate acyl complex
Cp(CO)2Fe + PhCOCl Cp(CO)2FePh
O
-CO
Fp Ph
8.2.1 Reactions of Metal alkyls

(i)  - hydride transfer
Methyl compounds like WMe6 decompose thermally to give CH4
and polymeric material.
WMe6 3CH4 + W(CH2)3
(ii)  - hydride transfer
H
H
CH2 CH2
LnM O LnM
O
(iii) γhydride transfer

H2 H2
C C
LnM SiMe2 LnM SiMe2
H CH2 C
H H2
H2
C
Mg(CH2SiMe3)
(Me3P)4 OS(COMe2)2 (Me3P)4 OS SiMe
- Me4Si
C
- Mg(CO2Me)2 H2
(iv) Intermolecular reductive eliminations
Ph3P Au Me + CH3 – CH3
102
Me
Me
PPh3 Au Me PPh3 Au Ph3P Au Me + CH3 - CH3

Me
Me Me
(v) Alkyl exchange reactions

NOTES
(Me3P)2(PhN)ReMe3+ (Me3P)2(PhN)ReCl3 (Me3P)2(PhN)ReCl2Me + (Me3P)2(PhN)ReClMe2
Empirical order of stabilities

The factors discussed above all influence the stability of metal alkyl
complexes. We can come up with some experimental observations about
the relative stabilities of different alkyl ligands:
a. 1-norbornyl > benzyl > trimethylsilyl > neopentyl > Ph ~ Me >>

Et (1o R) > 2, 3o R
Notice that norbornyl not only has a difficult time approaching the metal
center, but that the olefin that would be generated would be highly
strained (and violate Bent's rule).
b. Fluoroalkyl > alkyl (i.e. -CnF2n+1> -CnH2n+1)
CF bonds are very strong (120-130 kcal/mol vs. 98-104 kcal/mol for
alkyl C-H).
c. Chelating (metallacycles) > nonchelating (acyclic)
The dialkyl shown on the left decomposes at 110 oC with kdec = 1.0 s-1. In
contrast, the metallacycle has k = 5.3 x 10 -3 s-1. The beta-hydrogen has a
close approach to the metal in the dialkyl case, but not the metallacycle.
d. 3rd row > 2nd row > 1st row transition metals.
103
2MeI
Fe(CO)22- no isolable dialkyl, does give acetone
Organometallic Chemistry RT
but
Me
2MeI
Os(CO)2 2- Os CH4
RT Me 140 °C
NOTES
e. Strong electron-donating ligands increase stability.
Cp Cp
OC OC
Ph3P
OC
The carbonyl ligand reduces electron density on the metal through pi-
backbonding, in contrast to the phosphine ligand, which is a good sigma
donor.
General Methods of Synthesis of Metal Alkene Complexes
1) Substitution of CO in metal carbonyls or of weakly held ligands
by alkene. Cr(CO)6 + C7H8 → (η6 – C7H8)Cr(CO)3 + CO
Cl2Pd(RCN)2 + 2COD → Cl2 Pd (COD)2 + 2RCN
Ag+ + alkene [Ag (alkene)]+
2) From halides and other compounds in the presence of reducing

agents by use of anionic species.
Zn
RuF3(aq)+ 2 Cyclohexadiene → (η6 – C6H8) Ru (η4 – C6H8)
Ethanol
Al-terobu3
Ni(acac) + COD → (COD)2 Ni
(R3 P)2 PtCl2 + 2C2H4 → (R3P)2Pt (C2H4)2
3) CO – Condensation of metal vapours with alkene

Fe + 2COD → Fe (COD)2
4) Removal of a β – hydrogen from a coordinated alkyl ligand by

triphenyl carbonium ion
[Ph3C]+BF4
H
Fe 104 R
OC Fe
Self-Instructional Material C CH2R OC
OC HR
OC
H R
Simple alkyl ligands are dihapto two electron donars. The bond between
the ethylene molecule and metal ion is a dative σ – bond from the filled 
– orbital of the alkene to the suitably oriented metal orbital. The bonding
scheme is analogous to that in CO complexes. There is a L → M σ
donation and M → L * donation. i.e., NOTES
Two components
 -donation from alkene -orbital to metal -orbital (s, pz or dz2)
 -donation from metal d -orbital to alkene  * orbital
Evidence for this model?
-component: component:
C-C  empty metal orbital occupied metal empty C-C 
Note the similarity to CO ligands
component: donation of C lone pair
-component: backbonding into CO 
Structural data
(a) bond distances
105
NOTES
Zeise's salt
[PtCl3(C2H4)]-
C-C distance = 1.37Å
C-C distance in free ligand = 1.35Å
Conclusion : in this complex most of bonding is ligand  M -donation.
Both components strengthen M-C bonds and weaken C-C bonds, but -
donation has greatest effect in weakening C-C bond.
(b) bond angles

When backbonding occurs, hybridisation of alkene C- atoms changes
from sp2 to approaching sp3. This has an implication for the bond angles
(sp2 C-atom is planar sp3 C-atom is pyramidal)
So - substituents "bend-back" from the metal - the greater the
-donation the greater the bend-back.
C-C distances C2H4 = 1.35 Å

C2F4 = 1.40 Å
Rh-C distances C2H4 = 2.16 Å
C2F4 = 2.02 Å
More -donation in C2 F4 ligand because F atoms are electron
withdrawing.
CpRh(C2H4)(C2F4)
"Bend-back" angle C2H4 = 17o C2F4 = 37o
106
NOTES
Alkene complexes can also be thought of as metallacyclopropanes

Two approaches are complementary.
Hindered rotation of coordinated alkenes
Alkenes can rotate about M-C=C axis
 M - alkene -bond is invariant to rotation (does not affect overlap)
 M - alkene -bond is strongly dependent on rotation angle
Thus there is a energy cost (and hence a energy barrier) to this rotation.
Barrier is of the size which can be detected by variable temperature NMR
spectroscopy
Preparation of Zeises salt
W.C. Zeises isolated stable yellow crystals after refluxing an
alcoholic solution ofK2[PtCl4] in 1827 which is known as Zeises salt
K[Pt(C2H4)Cl3]
Zeises salt is now prepared by bubbling ethene through an
aqueous solution of potassiumtetrachloroplatinate(II) in the presence of
Sn(II) which aids the coordination sphere.
SnCl2
K2[PtCl4] + H2C = CH2 → K[Pt(C2H4)Cl3] + KCl
Structure of Zeises salt

A structural investigation of the anion in Zeises salt has shown that the
ethylene occupies the four –coordination sites of the square planar
complex with the C – C axis perpendicular to the platinum ligand
plane(Cl-Pt-Cl plane) ie., xy plane. Relative to free ethylene the C – C
bond is lengthened slightly from 1.35Å to 137.5 Å and the hydrogens are
slightly titled back from the planar arrangement.
The extent of back bonding depends on the metal substituents on
ethylene and the other ligands on the metal. For example in the
complexes of the type LRh (C2H4) (C2F4) where (L – acacorcp), the
tetrafluoroethylene molecule bonds more strongly and at a shorter
distance. Rh – C = 201 – 202 pm than the un substituted ethylene Rh –
C = 217 – 219 pm. This indicates that the  accepting ability of (C2F4>
C2H4) significantly influences the M – C bond in this compounds. Only
metal atoms in low oxidation states are sufficiently good  – donars to
stabilise alkene complexes.
107
Organometallic Chemistry Structure and Bonding
The bonding of an alkyne (acetylene) to a transition metal complex is
similar to that of an alkene complex. Alkynes tend to be more
electropositive and therefore tend to bind more tightly to a transition
metal than alkenes. In fact, alkynes will often displace alkenes.
NOTES The primary difference in bonding between alkenes and alkynes is that an
alkyne can act as either a 2 or 4 electron donor. Recall that alkynes have
two sets of mutually orthogonal pi bonds. We can bind one of these to
the transition metal in a sigma-type fashion (A) as we did for alkenes,
including a pi-backbond (B). The orthogonal set can also bind in a pi-
type fashion using an orthogonal metal d-orbital (C):
The back-donation to the antibonding orbital (D) is a delta-bond (there

are two nodes in it), and the degree of overlap is quite small as the two
orbitals meet side-to-side rather than engaging in direct overlap.
Therefore, the contribution of D to the bonding of alkynes is minimal at
best.
The net effect of this additional pi-donation is that alkynes are usually
non-linear when coordinated to a transition metal complex. We can draw
several resonance structures that depict the bonding of an alkyne. Iis the
metallacyclopropene resonance form. Support for this versus a simple
two electron donor, II, can be inferred from the C-C bond distance as
108
well the R-C-C-R angles (see below). III generally does not contribute to
the bonding of alkyne complexes.
NOTES
Other than geometry, the other major difference between I and II is that I
implies the metal oxidation state is greater by two. In other words, one
can sometimes think of alkynes as dianionic ligands instead of as neutral
ligands! Remember that electron counting is strictly a formalism.
As expected from the reduced C-C bond order, the C-C bond distances
for coordinated alkynes are typically larger (125 to 135 pm) than in the
uncoordinated ligand (110 to 115 pm).
For 4-electron donors, the R-C-C bond angles are usually in the range of
130 to 146 degrees, with M-C bond distances of 199 to 209 pm. The C-C
triple bond of free alkynes are normally observed around 2200 cm-1 in
the infrared or Raman spectrum.
Coordination to a transition metal reduces the C-C bond order,
leading to a lower stretching frequency in the range of 1700 to 2000 cm-1.
4-electron donors reflect their reduced nature in the IR: coordinated
internal alkynes are typically 1730 - 1820 cm-1 and coordinated terminal
alkynes are typically 1675 - 1715 cm-1.
Remember that symmetric C-C stretches are not IR active, so that an

asymmetric alkyne or the use of Raman spectroscopy may be required to
observe this spectroscopic feature. In an alkyne molecule such as
acetylene there are two mutually perpendicular  bonds. Acetylene can
use one  bond and the associated * orbital in exactly the same way as
found in olefin complexes.
This results in the lengthening of C – C bond distance and marked

deviation from linearity.
R
R
C
~135 to 150° C
~ 140°
M 126 to 130 pm M 133pm
C
C
R
R
(a) (a)
109
An alkyne can also behave as formal four electron donar to one metal
atom. In addition to the above discussed interaction, the other pair of 
electrons may be partially donated to a metal d  orbital lying
perpendicular to the plane of three membered ring. Again a synergestic
back donation may also occur if there is filled d – orbital perpendicular to
both of the already used (fig b). This leads to even greater lengthening of
NOTES C – C distance. Additional arrow is used to to represent this four electron
bonding.
Finally, it is worth noting that alkynes can also bridge two metal centers.
In these cases it is sometimes appropriate to describe the complex as a
1,2-dimetallatetrahedrane. In this case, the alkyne is a 2-electron donor to
each metal center:

Coordination of alkynes permits the trapping of alkynes that would not
ordinarily be stable. Consider this isolation of a benzyne complex
As one might expect, such species can act as a stoichiometric source of

benzyne and display a correspondingly rich reaction chemistry and
rearrangement of terminal acetylene complexes to the vinylidene
tautomer is common noticed reaction.
8.6 Metal – Arene Complexes

Arenes also form a variety of mono complexes that can be made
by reactions such as.
C6H6+ Mn(CO)5Cl + AlCl3 [C6H6Mn(CO)3] [AlCl4] + 2CO
CO + 2C6F5Br + C6H5Me ( -MeC6H5) CO(C6F5)2
110
The rings of the dibenzene chromium, molybedenum and
tungsten complexes are eclipsed and have a small rotational barrier.
Unlike ferrocene, these complexes have labile rings which can be Organometallic Chemistry
displaced.
Cr(CO)6 +  2  NOTES
Cr Cr
CO  CO
CO
The benzene rings can be removed completely by reaction

with a more active ligand.
Cr (6 - C6H6)2 + 6 PF3 Cr (PF3) + 2C6H6
Other arene bonding modes.
CpV-H -VCp
H
1. What is meant by Hapticity?
2. How will you synthesis metal alkyl complexes
3. Give example for  - hydride transfer of metal alkyl complexes
4. Dewar-Chatt approach to bonding in olefins
 The term hapticity is used to describe how a group of contiguous
atoms of a ligand are coordinated to a central atom. ηn: n = the
number of contiguous atoms of the ligand that are bound to the
metal
 Metal alkyl complexes are prepared by taking advantage of the
nucleophilicity of a carbonylate ion.
[Mn(CO)5]- + MeI  Me Mn (CO)5 + I –
 Methyl compounds like WMe6 decompose thermally to
give CH4 and polymeric material. WMe6 3CH4 +
W(CH2)3
 Two components
-donationfrom alkene -orbital to metal -orbital (s, pz or dz2)
-donationfrom metal d -orbital to alkene  * orbital.
111
8.9 Summary
Organometallic Chemistry Organometallic compounds: Compounds that contain a metal-carbon
bond, R-M, are known as "organometallic" compounds.
Zeise's salt: [PtCl3(C2H4)]-
Dewar-Chatt approach to bonding in olefins: In this complex most of
bonding is ligand  M -donation. Both components strengthen M-C
NOTES bonds and weaken C-C bonds, but -donation has greatest effect in
weakening C-C bond.
Metal – alkyne complexes: The primary difference in bonding between
alkenes and alkynes is that an alkyne can act as either a 2 or 4 electron
donor.
Metal arene complexes: Arenes also form a variety of mono
complexes that can be made by reactions such as.
C6H6 + Mn(CO)5Cl + AlCl3 [C6H6Mn(CO)3][AlC14] +
2CO
8.10 Keywords
Organometallic compounds: Compounds that contain a metal-carbon
bond, R-M, are known as "organometallic" compounds.
Hapticity: The term hapticity is used to describe how a group of
contiguous atoms of a ligand are coordinated to a central atom.
Metal – Arene Complexs: Ferrocene is the best known Metal – Arene
Complexes.
1. Define Organometallic compounds
2. Explain Hapticity
3. How will you synthesis metal alkyl complexes
4. How will you synthesis metal alkene complexes
5. How will you synthesis metal alkyene complexes
6. Explain Dewar-Chatt approach to bonding in olefins
1. Dewar, M. Bull. Soc. Chim. Fr. 1951, 1 8 , C79

2. J. Chatt and L. A. Duncanson, Olefin co-ordination compounds.
Part III. Infra-red spectra and structure: attempted preparation
of acetylene complexes J. Chem. Soc., 1953, 2939.
3. Buchwald and coworkers (Organometallics1993, 12 4182):
4. Jones, W. M.; Klosin, J. Adv. Organomet. Chem.1998, 42, 147.
112
UNIT-9 METALLOCENES
Structure Metallocenes
9.0 Introduction
9.1 Objective
9.2 Comparison of ferrocene with other metallocenes with respect to
their reactivity
9.3 Molecular orbital diagram of Ferrocene NOTES
9.4 preparation of Ferrocene (5–C5H5)2Fe

9.6 Fluxional Molecules
9.9 Summary
9.10 Keywords
9.0 Introduction
Metallocenes
A metallocene consists of a metal atom between two planar
polyhapto rings and they are called sandwich compounds. Example
ferrocene Fe((5-C5H5)2, bis(benzene) Chromium(0) Cr(6-C6H6)2 and
uranocene U(8-C8H8)2. The name metallocenes arose because they
participated in reactions similar to those of aromatic molecules.
Fe Cr U
Fe(5-C5H5)2 Cr(6-C6H6)2 U(8-C8H8)2
Some cyclic polyenes are known to form complexes in which

they are bound to a metal atom through some but not all of their carbon
atoms. In these cases the ring is non – planar. Besides these homoleptic
cyclopolyene complexes in which organometallic such as halogens, CO,
RNC and R3P share the coordination sphere of the metal with a cyclic
polyene.
eg. ( – C5H5)Mn(CO)3, ( – C5H5)Fe(CO)2Cl
There are also molecules in which two different types of

arene rings are present, such that the total number of  electrons
113
they provide plus those possessed by the metal atom itself add to 18 for
eg.
Metallocenes
NOTES Co
Mn
Co(5-C5H5)2
9.1 Objective
The main objective of this unit is to discuss the importance of
metallocene. After going through this unit you will be able to:
 Discuss the ferrocene with other metallocenes
 Describing Molecular orbital diagram of Ferrocene
 Discuss behavior of Fluxional Molecules
9.2 Comparison of ferrocene with other metallocenes with respect
to their reactivity
Ferrocene was the first of many complexes which came to be known as
metallocenes. The name arises because they participated in reactions
similar to those of aromatic molecules.
eg.
Cr Cr Mn Fe Co U Lu
All of the complexes except the last two obey the 18 – electron rule.
In addition to ferrocene, M(5–C5H5)2 compounds are known for
most of the other elements of the first transition series. (M = V, Cr, Mn,
Co, Ni) and these cannot obey the 18 – electron rule.
Ferrocene shows exceptional thermal stability (Stable to 500oC) and is
not oxidized by air. Furthermore cobaltocene, a 19 electron species, is
readily oxidized to the 18 – electron cobaltcenium ion [CO (5 – C5H5)2]
+
which reflects much of the thermal stability of ferrocene.
Among the mixed cyclopentadienyl carbonyl complexes
[(5 – C5H5)V(CO) 4], [(5 – C5H5)) – Cr(CO)3]2
[(5 – C5H5)Mn(CO) 3], [(5 – C5H5)) – Fe(CO)2]2,
[(5 – C5H5) Co(CO) 2], and [(5 – C5H5) Ni (CO)]2
Self-Instructional Material 114

The odd atomic number elements (V, Mn and Co) form
monomers and the even atomic number elements (Cr, Fe and Ni) form
dimers, which is in direct contrast to the behaviour shown by the simple Metallocenes
carbonyl complexes.
9.3 Molecular orbital diagram of Ferrocene
The semiquantitative energy level diagram for ferrocene is
shown. The set of ligand group orbitals (LGOS) in cyclopentadienyl in NOTES
the left hand side of the diagram rings are also shown.
The a1g () orbitals of cyclopentadiene are so stable relative to the
metal orbitals that they interact but little (ie., the ligand is a poor 
donar). The e2g () orbitals are so high in energy compared to the metal
orbitals of the same symmetry, that they interact very little (ie., these
empty orbitals are not good  acceptors). The elu and a2u (4p) orbitals on
the iron atom are at a high energy and so these orbitals do not contribute
much to bonding. The only orbitals that are well matched are e 1g ring and
metal (3d) orbitals which from two strong  bonds. These cp – Fe 
bonds are believed to supply most of the stabilization that holds the
ferrocene molecule together.
In ferrocene, there are 18 valance electrons to be accommodated.
Five  electrons from each C5H5 ring and eight valance electrons from
Fe atom. There are 9 bonding or non – bonding molecular orbitals and
ten antibonding molecular orbitals atom are shown in the right hand side
of the diagram. The ring  orbitals and the metal valence orbitals are
linearly combined in the form of molecular orbitals shown in the centre
of the diagram.
115
Metallocenes
NOTES
Ligand group orbitals and matching atomic orbitals on iron for

ferrocene

Metallocenes
NOTES
Qualitative molecular orbital diagram for a metallocene

Hence the 18 electrons can just fill the bonding and non –
bonding molecular orbitals giving a closed configuration.
The 18 – electron rule is a reflection of filling strongly stabilized
molecular orbitals. In manganocene, chromocene and vanadocene are
one, two and three electrons short of 18 while cobaltocene and
nickelocene have one and two electrons in excess of 18. So all are
paramagnetic except ferrocene.
The MO diagram is very much useful in understand the rule
violations and the magnetic properties.
The highest occupied molecular orbitals (e2g and e1g) are only
slightly bonding and therefore removing electrons from them does not
greatly destabilize the complex. The e1g LUMO is not significantly anti
bonding so when electrons are added to create 19 – electron and 20 –
electron species the stability loss is minimal.
9.4 preparation of Ferrocene (5–C5H5)2Fe
Bis (pentahaptocyclopentadienyl)Iron(II). Ferrocene has a sandwich
structure, in which Fe2+ is sandwiched between two cyclopentadienyl
ions. It is an orange red crystal with melting point 174 oC
117
i) C5H6 + Na  C5H5- + Na + ½ H2
Metallocenes
2C5H5- + Fe2+ (5 – C5H5) 2 Fe
ii) Fe + 2(R3 NH) Cl  FeCl2 + 2R3N + H2
FeCl2 + 2C5H6 + 2R3N  Fe (5 – C5H5) 2 + 2(R3NH) Cl
Net reaction : Fe + 2C5H6  Fe (5 – C5H5) 2 + H2
NOTES
The C–C bond orders in 5–C5H5 compounds resemble those of
benzene. Ferrocene is stable and maintain the ligand metal bonds under
harsh conditions, hence it is possible to carry out a variety of
transformations on the cyclopentadienyl ligands. The cyclopentadienyl
rings in ferrocene are aromatic and undergo many of the same reactions
of benzene.
Ferrocene is more reactive than benzene towards electrophilic
reagents, indicating that electrons are more readily available.
Acylation
Acylation of ferrocene by acetic anhydride containing phosphoric

acid as catalyst gives the acetyl derivatives of ferrocene.
O
C CH3
(CH3CO)2O
Fe
Fe + CH3COOH
H3PO4
Acetylferrocene
Acetylation of acetyl ferrocene

Acetylation of acetyl ferrocene deactivatives the molecule. In
order to obtain the diacetyl compound conditions similar to the usual
acylation of aromatic rings are required.
O O
C CH3 C CH3
(CH3CO)2O/AlCl3
Fe Fe
O
C CH3
Acetylferrocene 1,1`-diacetylferrocene

Metallation
Ferrocene reacts with n – butyl lithium to give monolithio and
dilithio derivative of ferrocene. Metallocenes
C6H6 + Li C4H9 Li C6H5 + C4H10
NOTES
Li Li
n-BuLi n-BuLi
Fe Fe Fe
Li
monolithioferrocene dilithioferrocene
Nitration
Direct nitration is not feasible as ferrocene is sensitive to
oxidation. However the nitro derivative can be made indirectly.
LI
NO2 NH2
Fe
N2O4 Reduction
Fe Fe
[H]
Fe/HCl
Carboxylation
Ferrocene reacts with n CO2/H2O to ferrocene carboxylic acid
COOH
CO2
Fe Fe
H2O
B(OH)2 Br
B(OR)3 CuBr
Fe Fe Fe
H2O
119
Metallocenes 9.6 Fluxional Molecules
Fluxional Molecules possess more than a single configuration
representing an energy minimum. Fluxionality is characteristic of certain
classes of organometallic compounds. The phenomenon is seen
characteristically in compounds containing conjugated cyclic polyolefins
NOTES such as cyclopentadienyl. cycloheptadienyl or cyclooctateraene, the three
most common ones, attached to a metal atom through at least one but less
than all of their carbon atoms.
Nuclear magnetic resonance techniques have proved to be
particularly valuable in the study of fluxional molecules. If the
interconversion process between them is slow on the NMR time scale, as
might be the case at low temperature, two separate sets of equal –
intensity resonances, one for each configuration will be observed in the
spectrum.
If we can raise the temperature of the sample sufficiently so that
the process becomes rapid on the NMR time scale, the result will be a
singlet and it will be appear at the midpoint of the two sets observed at
lower temperature. At this high temperature limit, the molecule is
undergoing changes so rapidly that NMR cannot distinguish the two
separate molecular configurations, only an average.
Consider (1 –C5H5)2 (5–C5H5)2Ti. The crystal structure of the
molecule shows two monohapto and two pentahapto cyclopentadienyl
rings.
At 62 oC, the 1HNMR spectrum consists of a single line,
consistent with a dynamic process that renders the four ligands
equivalent. As the temperature is lowered, the signal broadens and
gradually split into two lines which sharpen into equal intensity singlets
at – 27 oC. At this point, the process which interconverts mono and
pentahapto ligands is occurring slowly enough that both configurations
are observable in the spectrum.

Proton NMR spectra of (1 – C5H5)2 (5 – C5H5)2Ti from – 27 to +
620C
Metallocenes
1 3 3
1
Ti Ti etc NOTES
2 4 2 4
1 o o
H NMR spectra of (tetramethylallene)Fe(CO) at -60 C and 30 C
4
(tetramethylallene is Me2C=C=CMe2) low temperature spectrum: the
integrated ratios of the peaks are 1:1:2. it is not plausible for the allene to
coordinate only via its central carbon atom because that carbon has no
orbitals available to do this. The two of methyl groups (C) are
chemically equivalent the other two (A and B) are not equivalent: one
points at the metal and one away. At elevated temperature
intramolecular process occur and the allene is "hopping" from one  face
of the allene to another.
H3C CH3 H3C CH3
Fe(CO)4
C C
Fe(CO)4
H3C CH3 H3C CH3
Migration of iron in tetracarbonyltetramethyl

121
Metallocenes 1. Define Metallocene
2. Write the equation for synthesis of ferrocen
3. Describe properties of ferrocene?
4. Explain Fluxional Molecules
NOTES  A metallocene consists of a metal atom between two planar
polyhapto rings and they are called sandwich compounds
 C5H6 + Na  C5H5- + Na + ½ H2
2C5H5- + Fe2+ (5 – C5H5) 2 Fe
 Acylation of ferrocene by acetic anhydride containing phosphoric
acid as catalyst gives the acetyl derivatives of ferrocene.
Ferrocene reacts with n – butyl lithium to give monolithio
and dilithio derivative of ferrocene.
 Fluxional Molecules possess more than a single configuration
representing an energy minimum. Fluxionality is characteristic of
certain classes of organometallic compounds.
9.9 Summary
 A metallocene consists of a metal atom between two planar
polyhapto rings and they are called sandwich compounds.
 Ferrocene was the first of many complexes which came to be
known as metallocenes.
 Ferrocene is more reactive than benzene towards electrophilic
reagents, indicating that electrons are more readily available.
 Fluxional molecules possess more than a single configuration
representing an energy minimum. Fluxionality is characteristic of
certain classes of organometallic compounds.
1. What is meant by sandwich compound?
2. Explain the structure and bonding of ferrocene
3. Explain the dynamic behavior of organometallic compound?
1. Inorganic Chemistry,. G. S.Sodhi; 1stEdition, VB (P) Ltd, 2006.
2. Inorganic Chemistry, D. F. Shriver and P. W. Atkins, Oxford U.K.,
1999.
3. Modern aspects of Inorganic chemistry, H.J. Emelius and Sharpe,
Universal book Stall, New Delhi, 1989.
4. Inorganic Chemistry- Principles of structure and reactivity, J.E.
Huheey, E.A. Keiter and R.L. Keiter, 4th edition, Pearson-Education,
2002.
5. Advanced Inorganic Chemistry - F.A. Cotton and G. Wilkinson,
Wiley Eastern, 5thedition, 1998.
6. Chemistry & Chemical Reactivity, John C. Kotz, Paul M.
Treichel, John Townsend, 8thed., USA, 2012.

UNIT-10 METAL CARBONYL STRUCTURE
10.0 Introduction Metal Carbonyl Structure
10.1 Objectives
10.2.3 Structure M-C bond NOTES
10.3 Metal Carbonylate Anions
10.8 Keywords
10.0 Introduction
The π-bonding in complexes was proposed for the first time, by
Pauling (1924), in the form of back-bonding (ML) to account for
electro-neutrality of metal to ligand bond. According to him, if the
ligand, linked with the metal ion through LM, -bond, has vacant π-
orbitals, it can accept lone pair of electrons from metal-ion (if present) to
form ML, π- bonds. This also accounts for the extra stability of metal
complexes with unsaturated ligands. However the latest and the most
successful theory of bonding for metal-complexes Ligand Field Theory
(LFT), explained quantitatively while Mπ-bonding stabilizes, the
complex, LM π-bonding destabilize it. This also explains positions of
CN- and F- ligands in the spectrochemical series.
Most transition metals form complexes with a wide variety of
unsaturated molecules such as carbon monoxide, nitric oxide, dinitrogen,
dioxygen etc. In many of these, the metal is in zero or another low
oxidation state and, as we have already mentioned, π-bonding between
the metal and the ligands is believed to play an important part in
stabilizing these complexes. In this regard metal carbonyls are important
as they involve both metal carbon ϭ and π-bonds. In this unit we shall
consider the metal carbonyls, anions derived from them, some of their
substitution product, and complexes formed by a few other ligands.
Metal carbonyl compounds were first synthesized in 1868. Although
many compounds were produced, they couldn‘t be fully characterized
until the development of X-ray diffraction, and IR and NMR
spectroscopy. Metal carbonyl compounds typically contain metals in the
zero oxidation state. In general, these compounds obey the ―18 electron
rule.‖ Although there are exceptions, this rule can be used to predict the
structure of metal carbonyl cluster compounds, which contain metal-
metal bonds. Many transition metal carbonyl compounds obey the 18-
123
electron rule. The reason for this can be readily seen from the molecular
orbital diagram of Cr(CO)6. The σ donor and π acceptor nature of CO as
Metal Carbonyl Structure
a ligand results in an MO diagram with greatest stability at 18 electrons.
10.1 Objectives
The main aim of this unit is to study π-complexes of transition
metals, with special reference to bonding and their structures. After going
NOTES through this unit you should be able to:
 describe metal carbonyls, their classification, methods of
preparation and reactions; with special reference to their
structures,
 discuss how these complexes, almost without exception, conform
to the effective atomic number rule and isoloble concept,
 explain bonding in these complexes in terms of IR spectra;
 describe preparation, properties and structures of metal nitrosyls,
The compounds formed by the combination of CO molecules
with transition metals are known as metallic carbonyls. Carbon mono-
oxide posses a unique property of unsaturation by virtue of which it may
combine with a large number of metals under suitable conditions. Such
compounds of CO with metals are termed as metallic carbonyls. In
carbonyls, a metal atom is directly linked to the carbon atom of a
carbonyl group. Since the electrons forming OCM bond are supplied
solely by CO molecule, metal atom in carbonyls is said to be in zero
oxidation state. In metal carbonyls CO molecules act as neutral ligands.
Metal carbonyls vary considerable in their properties ranging from
volatile nonpolar to the nonvolatile electrovalent carbonyls. For example-
nickel forms volatile nonpolar carbonyls, where as alkali and alkaline
earth metals from non-volatile electrovalent carbonyls.
The general formula of the carbonyls may be given as Mx(CO)y where
M is a metal capable of forming carbonyl. Metal carbonyls may be
regarded as parents of number of related compounds such as metal
nitrosyl carbonyl, M (NO)y (CO)x, and metal carbonyl hydrides HxM
(CO)y.
Carbonyls are classified into two distinct groups:
1) Monocular carbonyls: These carbonyls have the general formula
Mx(CO)y which contain more than one metal atom per molecule.
2) However the carbonyls having 2 metal atoms are called
binocular carbonyls, and
3) those having more than two metal atoms as ploynuclear
carbonyls. Polynuclear carbonyls may be homonuclear e.g.
[Fe3(CO)12 or heteronuclear e.g. MnCo(CO)9, MnRe(CO)10]
They have following characteristics:
i. These are almost insoluble in organic solvents.
ii. Many polynuclear carbonyls decompose at or below the
2) melting point.
124
a. Direct synthesis
1. Nickel reacts with CO at room temperature and normal
pressure;
40 °C
Ni + 4CO Ni(CO)4
NOTES
2. When CO is passed over reduced iron at 108°-220°C and pressure of
50 to 200 atm pressure. Fe(CO)5 is formed;
Fe + 5CO Fe(CO)5
Rhenium, osmium and iridium carbonyls could not be prepared by direct
reactions.
b. Indirect synthesis involving the Grignard reagent:
Job prepared chromium hexacarbonyl by the action of CO on a
mixture of grignard reagent and anhydrous chromium chloride in ether
solution. According to Hiber the primary reaction is as follows:
C6H5MgBr + CrCl3 + CO Cr(CO)2(C6H5) + MgBrCl + MgBr2
The unstable intermediate compound is composed with acid to yield the

hexacarbonyl:
3Cr(CO)2(C6H5)4 + 6H+  Cr(CO)6 + 2Cr3+ + 12C6H5- + 3H2
The reactions gives low yield which can be improved by using high
carbon mono-oxide pressure.
c. Indirect synthesis involving metal compounds: Metal carbonyls can

be prepared by the reaction of CO with certain metal compounds for
example:
i. Nickel tetracarbonyl may be prepared by passing CO into a suspension
of nickel cyanide, sulphide or mercaptide suspended in NaOH solution.
2NiX4 + 2nCO 2Ni(CO)nX + X2
Ni(CO)nX + (4-2n)CO Ni(CO)4 + NiX2
Synthesis from other carbonyls: when iron pentacarbonyl is exposed to

UV light it loses CO and forms Fe2(CO)9. This compound undergoes
thermal decomposition to yield iron pentacarbonyl and trimeric
tetracarbonyl.
UV
2Fe(CO)5 Fe2(CO)4 + CO
heat
2Fe2(CO)9 Fe(CO)5 + [Fe(CO)4]3 + CO
125
Properties of Carbonyls
 The metal carbonyls are crystalline solids, except for nickel
carbonyl and the pentacarbonyls of iron, ruthenium and osmium
which are liquids.
 Many are coloured for example: Crystals of cobalt carbonyl are
orange and iron pentacarbonyls is yellow oil and nicked
NOTES carbonyl is colourless.
 Due to their covalent nature renders them insoluble in water,
most of them are soluble in solvents like CCl4.
 Excepting V(CO)6 all the carbonyls are diamagnetic. V(CO) 6 is
paramagnetic and its paramagnetic property corresponds to the
presence of one unpaired electron. The metal in carbonyls are in
zero oxidation state.
Chemical Properties
1. Substitution Reactions: Some or all CO groups present in carbonyls
can be replaced by monodentate ligands such as alkyl or aryl isocyanide
(CNR) PR3, PCl3, Py, CH3OH etc.
Ni(CO)4 + 4CNR  Ni(CNR)4 + 4CO
Ni(CO)4 + 4PCl3Ni(PCl3)4 + 4CO
Fe(CO)5 + 2CNRFe(CO)3(CNR)2 + 2CO
Substitution reactions of metal carbonyls frequently indicate differences

in bonding characteristics of ligands. In the case of Mn(CO) 5Br,
radiochemical tracer studies have shown that only four CO groups
undergo exchange with 14CO.
Mn(CO)5Br + 414CO  Mn(14CO)4(CO)Br + 4 CO
The four CO molecules that undergo exchange reactions are those in the
plane, which are all transto each other. This indicates that the CO transto
Br is held more tightly because Br does not compete for π bonding
electron density donated from Mn. In the case of the other four CO
groups, competition between the groups, which are all good acceptors,
causes the groups to be labilized
2. Action of NaOH or Na metal: Formation of carbonylate ion:

Aqueous alcoholic solution of NaOH reacts with Fe(CO)5 to form
carbonylate anion [Fe(CO)4]-.
[Fe(CO)5] + 3NaOH → Na[Fe(CO)4H] + Na2CO3 + H2O
H-atom in [Fe(CO)4H]- ion is acidic which implies that Fe atom in this

ion is in -2 oxidation state.
Na-metal in liquid NH3 is able to convert Fe2(CO)9. Co2(CO)8,
Fe3(CO)12, Cr (CO)6,.Mn2(CO)10 etc, into carbonylate anions and in this
conversion these carbonyls are reduced.
Fe2(CO)9 + 4Na  2Na[Fe2-(CO)4]2- + CO
126
Co2(CO)8 + 2Na  2Na+[Co-(CO)4]4
3. Action of halogens: Most of the carbonyls react with halogens to yield Metal Carbonyl Structure
carbonyl halides. For example:
Fe(CO)5 + X2 Fe(CO)4X2 + CO
Mo(CO)6 + Cl2 Mo(CO)4Cl2 + 2CO
Mn2(CO)10 + X2(X = Br, I)  2Mn(CO)5X NOTES
Both Co2(CO)6 and Ni(CO)4 are decomposed into metallic halides and
CO when treated with halogens.
Co2(CO)8 + 2X2 2CoX2 + 8CO
Ni(CO)4 + Br2 NiBr2 + 4CO
Reactions of metal carbonyls with halogens lead to the formation of
carbonyl halide complexes by substitution reactions or breaking metal-
metal bonds.
The reaction
[Mn(CO)5]2 + Br2 → 2 Mn(CO)5Br
involves the rupture of the Mn–Mn bond, and one Br is added to each
Mn.
4. Action of NO: Many carbonyls react with nitric oxide (NO) to form
metal carbonyls nitrosyls. For example:
95 °C
Fe(CO)5 + 2NO Fe(CO)2(NO)2 + 3CO
3Fe3(CO)9+4NO 2Fe(CO)2(NO)2+ Fe(CO)5+Fe3(CO)12+ 6CO
The nitric oxide molecule has one unpaired electron residing in an
antibonding π * molecular orbital. When that electron is removed, the
bond order increases from 2.5 to 3, so in coordinating to metals, NO
usually behaves as though it donates three electrons. The result is
formally the same as if one electron were lost to the metal,
NO → NO+ + e-
followed by coordination of NO+, which is isoelectronic with CO and
CN. Because NO+ is the nitrosyl ion, the products containing nitric oxide
and carbon monoxide are called carbonyl nitrosyls . The following
reactions are typical of those producing this type of compound:
Co2(CO)8 + 2 NO → 2 Co(CO)3NO + 2 CO
Fe2(CO)9 + 4 NO → 2 Fe(CO)2(NO)2 + 5 CO
[Mn(CO)5]2 + 2 NO → 2 Mn(CO)4NO + 2 CO
It is interesting to note that the products of these reactions obey the 18-
electron rule
4. Disproportionation
A number of metal carbonyls undergo disproportionation reactions in the
presence of other coordinating ligands. For example, in the presence of
amines, Fe(CO)5 reacts as follows:
2Fe(CO)5 +6 Amine → [Fe(Amine)6]2+ [Fe(CO)4]2- + 6 CO
127
This reaction takes place because of the ease of formation of the
carbonylate ions and the favorable coordination of the Fe 2+ produced.
The reaction of Co 2(CO)8 with NH3 is similar.
Co2(CO)8 + 6 NH3 → [Co(NH3)6][Co(CO)4]2
NOTES Formally, in each of these cases the disproportionation produces a

positive metal ion and a metal ion in a negative oxidation state. The
carbonyl ligands will be bound to the softer metal species, the anion; the
nitrogen donor ligands (hard Lewis bases) will be bound to the harder
metal species, the cation.
These disproportionation reactions are quite useful in the preparation of a
variety of carbonylate complexes. For example, the [Ni2(CO)6]2 ion can
be prepared by the reaction
3 Ni(CO)4 + 3 phen → [Ni(phen)3][Ni2(CO)6] + 6 CO
The range of coordinating agents that will cause disproportionation is

rather wide and includes compounds such as isocyanides, RNC:
Co2(CO)8 + 5 RNC → [Co(CNR)5][Co(CO)4] + 4 CO
5. Action of H2: Formation of carbonyl hydrides (reduction): when

Mn2(CO)10 and Co2(CO)8 react with H2, they get reduced to carbonyl
hydrides, Mn(CO)5H and Co(CO)4H respectively.
200 °C
Mn2(CO)10 + H2 2[Mn(CO)5H]
200 atm
165 °C
Co2(CO)8 + H2 2[Co(CO)4H]
200 atm
6. Action of heat: Different carbonyls yields different products when
heated for example:
250 °C Fe + 5CO
Fe(CO)5
3Fe2(CO)9 70 °C 3Fe(CO)5 + Fe3(CO)12
140 °C
Fe3(CO)12 3Fe + 12CO
10.2.3 Structure M-C bond

128
According to MO theory, the bonding in metal carbonyl is
overlap of the filled orbital of carbon and σ – type orbital of the metal Metal Carbonyl Structure
atom to from a σ or dative bond. Electron flow in such a dative overlap
increases the electron density of the metal atom. The metal therefore
attempts to reduce this charge by pushing electrons back to the ligand. A
second dative overlap of a filled d  or hybrid dp metal orbital with an
NOTES
empty p  orbital or g* or 2  orbital on so.
This bonding mechanism is synergic. The drift of metal electrons

referred to as back bonding into CO orbital increases the lewis basicity
via the σ orbital of carbon. At the same time, the drift of electrons to the
metal in the σ – bond tends to make the CO positive, thus enhancing the
acceptor strength of the Π orbitals. Thus upto a point the effect of σ
bond formation strengthen the Π bonding and vice versa.
 bond  back bond
M C O M C O
empty filled filled d empty  *

p or d  orbital orbital orbital
orbital

IR spectra give important information regarding nature of carbonyl
groups present in metal carbonyl complexes. We can differentiate
between the terminal carbonyl e.g. in Mn2(CO)10 and bridging carbonyl
groups, as in Co2(CO)8. Metal-carbon distances in Fe2(CO)9 and
Co2(CO)8 fall into two groups, metal-bridging carbonyl distances being
about 0-1 Å longer than metal-terminal carbonyl distances. Such a
difference is compatible with the concept of two-electron donation by
terminal carbonyls, and one electron donation (to each of two metal
atoms) by bridging carbonyls, through the possible existence of  bonds
of different strengths makes quantitative interpretation impossible. That
the extent of  bonding to terminal and bridging carbonyls is different is
clearly shown by carbonyl stretching frequencies. Carbon monoxide
itself has stretching frequency of 2143 cm-1 ; neutral metal carbonyls
known to have no bridging carbonyl groups have stretching frequencies
in the range 2125-2000 cm-1 ; and Fe2(CO)9 and Co2(CO)8, in addition to
showing bands in this region, also show carbonyl absorption at 1830 and
1860 cm-1 respectively. In general, carbonyl absorption in the 1900-1800
cm-1 region is indicative of the presence of bridging carbonyl groups in
129
uncharged species, though the presence of other groups may result in the
lowering of the stretching frequencies of terminal carbonyl groups into
this region (in carbonylate anions such as [Co(CO) 4]- and [Fe(CO)4]2-
very low carbonyl stretching frequencies of 1883 and 1788 cm-1
respectively result from the strong metal-carbon -bonding which
stabilizes the low oxidation state of the metal. In a few neutral species
NOTES believed to contain carbonyl groups bonded to three metal atoms,
stretching frequencies of 1800 cm-1 or less are found.
Thus, in summary the terminal carbonyl absorption is obtained in
the range of 2125-2000 cm-1, while bridging carbonyl frequency is
obtained in the 1900-1800 cm-1 region. While, the strong metal carbon 
bonding is indicated by very low carbonyl structing frequencies of 1883
and 1788 cm-1 respectively.
Evidences for back bonding.

When there is back bonding M = C =O, the bond order is reduced
to 2 and hence the stretching frequency decreased from 2145cm-1(for M-
C≡O) to 2125-1850 cm-1.
CO N
OC CO N CO
OC CO N CO
CO CO
2100, 2000, 1985 cm-1 1900, 1760 cm-1
If we replace the CO (better  acceptor) by triamine (Poor  –

acceptor), the CO ligands receives large electron density from the metal
and the bond order increases. But the bond (C  O) order decreases and
has a low stretching frequency than Cr(CO)6.
Ni (CO)4, Co(CO)4, Fe (CO)42-
 2060 cm-1, 1890 cm-1 , 1790 cm-1
Because of the negative charge more and more electron density is
taken away by carbon atom. In order to stabilize the valancy of carbon,
the carbon – oxygen bond order decreases and stretching frequency
decreases.
[V(CO)6]- - 1860 cm-1

[Mn(CO)6]+ -  2090 cm-1
[Cr(CO)6] -  2000 cm-1
130
Terminal versus bridging carbonyls
O Metal Carbonyl Structure

M O
C
C
C M
M M M
O
M
terminal bridging  bridging 
 2 3 NOTES
CO 2120-1850 cm-1
1850-1700 cm -1 1730-1620 cm-1
Cp
Fe CO
O O
CO C C CO
OC
OC CO OC Fe Cp
Cr OC Fe Fe OC Fe
CO Cp
OC CO OC C CO
CO O Fe
Cp CO
2018, 1826 cm-1 1620 cm-1

2000 cm-1
Modes of Coordination of CO ligand
131
10.3 Carbonylate Anions
Metal Carbonyl Structure Several carbonylate anions such as Co(CO)4– , Mn(CO)5– , V(CO)6–, and
[Fe(CO)4]2– obey the EAN rule.
One type of synthesis of these ions is that of reacting the metal carbonyl
with a reagent that loses electrons readily, a strong reducing agent.
Active metals are strong reducing agents, so the reactions of metal
NOTES carbonyls with alkali metals should produce carbonylate ions.
The reaction of Co 2(CO)8 with Na carried out in liquid ammonia at 75°C
is one such reaction.
Co2(CO)8 + 2 Na → 2 Na[Co(CO)4]
Similarly,
Mn2(CO)10 + 2 Li → 2 Li[Mn(CO)5]
Although Co(CO)4 and Mn(CO)5 do not obey the 18-electron rule, the
anions Co(CO)4– and Mn(CO)5– do
A second type of reaction leading to the formation of carbonylate anions

is the reaction of metal carbonyls with strong bases.
For example,
Fe(CO)5 + 3 NaOH → Na[HFe(CO)4] + Na2CO3 + H2O
Cr(CO)6 + 3 KOH → K[HCr(CO)5] + K2CO3 + H2O
With Fe2(CO)9 , the reaction is
Fe2(CO)9 + 4 OH– → Fe2(CO)82– + CO32– + 2H2O

Metal carbonyl hydrides are complexes of transition metals with carbon
monoxide and hydride as ligands. These complexes are useful in organic
synthesis as catalysts in homogeneous catalysis, such as
hydroformylation.
132
Preparation
Walter Hieber prepared the first metal carbonyl hydride in 1931 by the
so-called Hieber base reaction of metal carbonyls. In this reaction a Metal Carbonyl Structure
hydroxide ion reacts with the carbon monoxide ligand of a metal
carbonyl such as iron pentacarbonyl in a nucleophilic attack to form a
metallacarboxylic acid. This intermediate releases of carbon dioxide in a
second step, giving the iron tetracarbonyl hydride anion. The synthesis of
cobalt tetracarbonyl hydride (HCo(CO)) proceeds in the same way. NOTES
Fe(CO) + NaOH → Na[Fe(CO)COH]
Na[Fe(CO)COH] → Na[HFe(CO)] + CO
A further synthetic route is the reaction of the metal carbonyl with

hydrogen. The protonation of metal carbonyl anions, e.g. [Co(CO)]−,
leads also to the formation of metal carbonyl hydrides.
Generally, carbonyl hydrides are obtained by acidifying solutions

containing the corresponding carbonylate anion or by the reactions of
metal carbonyls with hydrogen. The following reactions illustrate these
processes:
Co(CO)4–+ H+(aq) → HCo(CO)4
[Mn(CO)5]2 + H2 → 2 HMn(CO)5
Na[HFe(CO)4] + 2H+(aq) → H2Fe(CO)4 + Na+(aq)
Properties
The neutral metal carbonyl hydrides are often volatile and can be quite
acidic. The hydrogen atom is directly bounded to the metal. The metal-
hydrogen bond length is for cobalt 114 pm, the metal-carbon bond length
is for axial ligands 176 and 182 for the equatorial ligands.
Metal carbonyl hydrides are used as catalysts in the

hydroformylation of olefins. Under industrial conditions the catalyst is
usually formed in situ in a reaction of a metal salt precursor with the
syngas. The hydroformylation starts with the generation of a
coordinatively unsaturated 16-electron metal carbonyl hydride complex
like HCo(CO) or HRh(CO)(PPh) by dissociation of a ligand. Such
complexes bind olefins in a first step via π-complexation. In a second
step an alkyl complex is formed by insertion of the olefin into the metal-
hydrogen bond, leading once again to a 16-electron species. This
complex can bind another carbon monoxide, which can insert into the
metal-carbon bond of the alkyl ligand to form an acyl complex. By
133
oxidative addition of hydrogen and elimination of the aldehyde the initial
metal carbonyl hydride complex is regenerated.
The exact structure of the metal carbonyl hydrides has been
determined by using neutron diffraction and nuclear magnetic resonance
spectroscopy.
NOTES Metal nitrosyl complexes, have gained significant interest in the past
twenty years because of the important role nitric oxide displays as
signaling molecule in biological systems. Metal nitrosyl complexes are
complexes that contain nitric oxide, NO, bonded to a transition metal.
Many kinds of nitrosyl complexes are known, which vary both in
structure and coligand.
Most complexes containing the NO ligand can be viewed as
derivatives of the nitrosyl cation, NO+. The nitrosyl cation is
isoelectronic with carbon monoxide, thus the bonding between a nitrosyl
ligand and a metal follows the same principles as the bonding in carbonyl
complexes. The nitrosyl cation serves as a two-electron donor to the
metal and accepts electrons from the metal via back-bonding. The
compounds Co(NO)(CO)3 and Ni(CO)4 illustrate the analogy between
NO+ and CO. In an electron-counting sense, two linear NO ligands are
equivalent to three CO groups. This trend is illustrated by the
isoelectronic pair Fe(CO)2(NO)2 and [Ni(CO)4]. These complexes are
isoelectronic and, incidentally, both obey the 18-electron rule. The
formal description of nitric oxide as NO+ does not match certain
measureable and calculated properties. In an alternative description,
nitric oxide serves as a 3-electron donor, and the metal-nitrogen
interaction is a triple bond.
Linear vs bent nitrosyl ligands

The M-N-O unit in nitrosyl complexes is usually linear, or no more than
15° from linear. In some complexes, however, especially when back-
bonding is less important, the M-N-O angle can strongly deviate from
180°. The differing vibrational frequencies reflect the differing N-O bond
orders for linear (triple bond) and bent NO (double bond).
The bent NO ligand is sometimes described as the anion, NO −.
Prototypes for such compounds are the organic nitroso compounds, such
as nitrosobenzene. A complex with a bent NO ligand is trans-
[Co(en)2(NO)Cl]+.
134
O
O
N N
M M
Linear and bent M-NO bonds
M N O M N O M N O
NOTES
 Increasing strength of the p-back bond strengthens the M-N bond
and weakens the N-O bond.
 If the backbonding effect is weak, the angle decreases
significantly (< (M-N-O)= ~120 o) and the ligand can be
described as ―NO-―
 The Enemark-Feltham notation is used to describe the number of
d-type electrons present in a given metal nitrosyl complex.
Complexes with "d+ *-electrons" in excess of six often tend to
have bent NO ligands i.e., Co(NO)dtc2 (7 e,127o).
 Infrared spectroscopy and EPR spectroscopy can be used to
distinguish between different bond modes.
 Linear M-N-O groups (N-O triple bond) absorb in the range
1650–1900 cm−1 (i.e., [Fe(CN)5(NO)]2-: 1939 cm-1,
[Mn(CN)5(NO)]3-: 1700 cm-1)
 Bent nitrosyl groups (N-O double bond) absorb in the range
1525–1690 cm−1 (i.e., [Co(NH3)5(NO)]2+: 1620 cm-1).
Preparation
Nitrosyl complexes are typically prepared by treating reduced metal
complexes with nitric oxide. The nitrosylation of cobalt carbonyl is
illustrative
Co2(CO)8 + 2 NO → 2 CoNO(CO)3 + 2 CO
From nitrosonium sources

Replacement of ligands by the nitrosyl cation may be accomplished using
nitrosyl tetrafluoroborate, [NO]BF4. When applied to the hexacarbonyls
of molybdenum and tungsten, the NO binds to the metal
M(CO)6 + 4 MeCN + 2 NOBF4 → [M(NO)2(MeCN)4](BF4)2
Nitrosyl chloride and molybdenum hexacarbonyl react to give

[Mo(NO)2Cl2]n.Diazald is also used as an NO source.
Reactions
An important reaction is the acid/base equilibrium:
[LnMNO]2+ + 2OH−⇌ LnMNO2 + H2O
This equilibrium serves to confirm that the linear nitrosyl ligand is,
formally, NO+, with nitrogen in the oxidation state +3
135
NO+ + 2 OH−⇌ NO2− + H2O
Since nitrogen is more electronegative than carbon, metal-nitrosyl
complexes tend to be more electrophilic than related metal carbonyl
complexes. Nucleophiles often add to the nitrogen. The nitrogen atom in
bent metal nitrosyls is basic, thus can be oxidized, alkylated, and
NOTES protonated, e.g.:
(Ph3P)2(CO)ClOsNO + HCl → (Ph3P)2(CO)ClOsN(H)O
In rare cases, NO is cleaved by metal centers:

Cp2NbMe2 + NO → Cp2(Me)Nb(O)NMe
2 Cp2(Me)Nb(O)NMe → 2 Cp2Nb(O)Me + ½MeN=NMe
1. Explain π-back bonding
2. How will you prepare Ni(CO)4
3. Describe physical properties of metla carbonyl
4. How IR vibration spectra used to predict the structure of
Carbonyl complexes
if the ligand, linked with the metal ion through LM, -bond, has
vacant π-orbitals, it can accept lone pair of electrons from metal-ion (if
present) to form ML, π- bonds. This also accounts for the extra
stability of metal complexes with unsaturated ligands.
40 °C
Ni + 4CO Ni(CO)4
 The metal carbonyls are crystalline solids, except for nickel

carbonyl and the pentacarbonyls of iron, ruthenium and osmium
which are liquids.
 Many are coloured for example: Crystals of cobalt carbonyl are
orange and iron pentacarbonyls is yellow oil and nicked
carbonyl is colourless.
 Due to their covalent nature renders them insoluble in water,
most of them are soluble in solvents like CCl4.
 Excepting V(CO)6 all the carbonyls are diamagnetic. V(CO)6 is
paramagnetic and its paramagnetic property corresponds to the
presence of one unpaired electron. The metal in carbonyls are in
zero oxidation state.
 The terminal carbonyl absorption is obtained in the range of
2125-2000 cm-1, while bridging carbonyl frequency is obtained
in the 1900-1800 cm-1 region. While, the strong metal carbon 
bonding is indicated by very low carbonyl structing frequencies
of 1883 and 1788 cm-1 respectively.
136
10.8 Keywords
Metal nitrosyl:Metal nitrosyl complexes are complexes that contain
nitric oxide, NO, bonded to a transition metal. Metal Carbonyl Structure
Linear vs bent nitrosyl ligands: The M-N-O unit in nitrosyl complexes

is usually linear, or no more than 15° from linear.The bent NO ligand is
sometimes described as the anion, NO−.
NOTES
1. Give example for carbonylate anions
2. Write the structure of metal carbonlye hydrate
3. What is meant by π -back bonding
4. Explain the structure of metal nitrosyl complexes
10.10 Further reading
 Hayton, T. W.; Legzdins, P.; Sharp, W. B. (2002). "Coordination
and Organometallic Chemistry of Metal-NO Complexes". Chem.
Rev. 102 (1): 935–991.
 Holleman, Arnold Frederik; Wiberg, Egon (2001), Wiberg, Nils

(ed.), Inorganic Chemistry, translated by Eagleson, Mary;
Brewer, William, San Diego/Berlin: Academic Press/De Gruyter,
ISBN 0-12-352651-5
 W. Hieber, F. Leutert: Zur Kenntnis des koordinativ gebundenen

Kohlenoxyds: Bildung von Eisencarbonylwasserstoff. Die
Naturwissenschaften. volume 19, 1931, pp. 360–361,
 H. D. Kaesz,R. B. Saillant: Hydride Complexes of the Transition
Metals" Chem. Rev., 1972, volume 72, pp 231–281.
 Ralph G. Pearson The transition-metal-hydrogen bond. Chemical

Reviews. volume 85, 1985, S. 41–49.
 E. A. McNeill, F. R. Scholer: Molecular structure of the gaseous

metal carbonyl hydrides of manganese, iron, and cobalt. Journal
of the American Chemical Society. volume 99, 1977, S. 6243–
6249,
 F. A. Cotton: Structure and Bonding in Metal Carbonyls and

Related Compounds. In: Helvetica Chimica Acta. 50, 1967,
S. 117–130,
137
UNIT 11 CATALYSIS INVOLVING
Catalysis Involving
Organometallics ORGANOMETALLICS
Structure
11.0 Introduction
11.1 Objectives
NOTES 11.2 Oxidative addition
11.4 Hydrogenation
11.8 Isomerisation
11.11 Summary
11.12 Keywords
11. 0 Introduction
A thermodynamically favorable reaction may be slow at modest
temperatures and thus of little value for synthesis. Increased temperatures
may help making it faster, but competing reactions may be accelerated as
well. A more attractive approach to increase the rate of a reaction is to
use catalysis.
Catalysts are the substances which increase the rate of the reaction which
itself not consumed in the reaction. A catalyst typically increases the
reaction rates by lowering the activation energy by opening up pathways
with lower Gibbs free energies of activation (G).Sometimes, the thermal
reaction and the catalysed reaction give different products. This is
because the catalyst has accelerated a reaction that is normally kinetically
unfavourable. Generally, we will be interested in catalysts that increase
the rate of reaction, but it should be noted that inhibitors which slow
down certain reactions arealso of great commercial and academic
importance.
138
Catalysis Involving
Organometallics
NOTES
Catalytic efficiency of a catalyst is expressed in turn over number (N). In

catalysis, the term turnover number has two meanings: the number of
moles of substrate that a mole of catalyst can convert before becoming
inactivated and is the amount of substrate converted per the amount of
catalyst used. In theory, the Ideal catalyst would have an infinite turnover
number and would never be consumed. In practice, turnover numbers
begin at 100 and can go up to a million, more so in some cases. Further,
the turn over number N is defined as the velocity of the reaction V
divided by concentration of the catalyst [Q].i.e., N= V/[Q]. If N is high
the catalyst is good, because for small concentration of the catalyst, the
rate is high.
Turnover Frequency (TOF) A catalyst‘s turnover frequency
number, or turnover number per time unit, characterizes its level of
activity. So the TOF is the total number of moles transformed into the
desired product by one mole of active site per hour. Larger the TOF, the
more active the catalyst.
TOF = TON/hour
In catalysis by organometallic systems, the catalyst brings

together substrates within the coordination sphere. This means that the
catalyst must have a free coordination site, or at least be able to free-up a
coordination site by ligand dissociation or isomerisation. The substrates
are activated in some way by the process of coordination and a reaction
takes place. Often the most difficult step is that of decomplexation of the
transformed substrate. Indeed, although many "organic" processes can be
mediated by organometallics, relatively few are truly catalytic. This is
largely because the transformed fragment refuses to de-complex from the
metal centre in order to free-up a coordination site for the next substrate
molecule.
139
Thus the Mode of Action of Transition-Metal Complexes in Catalysis.
 The coordination of the reaction partners to a transition metal
Catalysis Involving
Organometallics brings them into close proximity, thus promoting the reaction.
 Through coordination to a transition metal, a reaction partner can
become activated for subsequent reactions.
 The coordination of an organic substrate to a transition metal can
NOTES facilitate nucleophilic attack.
 Catalytically active systems therefore must possess vacant
coordination sites or be able to generate them in a primary
dissociation step.
 Catalytic Cycles: The essence of catalysis is a cycle of reactions
that consumes the reactants, forms products and regenerates the
catalytic species. The catalytic cycle operates in the principle of
microscopic reversibility. i.e., If a certain series of steps
constitutes the mechanism of a forward reaction, the mechanism
of the reverse reaction is given by the same steps traversed
backwards. (applies only to thermal reactions and not-
photochemical reactions) The sequence of transition states and
relative intermediates in the mechanism of a reversible reaction
must be the same but in reverse order for the backward reaction
as for the forward reaction
We will discuss the most well studied and/or useful examples of

homogeneous catalysis: olefin hydrogenation (addition of hydrogen
across C=C bond) olefin hydroformylation (addition of hydrogen and
formyl HC(O) across C=C bond) olefin metathesis olefin polymerization
carbonylation of methanol (Monsanto acetic acid process)Olefin
hydrogenation. The following reaction is favorable but does not proceed
at all at room temperature: In the beginning of the 20th century Paul
Sabatier discovered that hydrogenation of olefins can be accelerated with
finely dispersed Ni, Pt or Pd (heterogeneous catalysis).If hydrogenation
of substrates with many functional groups in them is needed,
heterogeneous catalysis is not a good choice because of the lack of
selectivity:
11.1 Objectives
The main aim of this unit is to discuss the importance of organotransition
metal complexes as catalysts in different industrially important reactions.
After going through this unit you will be able to:
 Discuss the reactions taking part in the mechanism of catalytic
reactions of organotransition metal complexes, such as oxidative
addition reaction
 Describing hydrogenation, polymerization and Hydroformylation
etc., reactions, can discuss the mechanism of catalytic part played
by organotransition metal complexes in industrially important
reactions
 Discuss the mechanisms of Zeiglar – Natta and Wacker process
140
11.2 Oxidative addition
Catalysis Involving
Oxidative addition (or oxad) reaction which are useful for establishment Organometallics
of new transition metal-carbon -bonds involve the oxidation (i.e.,
increase in the formal oxidation number), accompanied by an increase in
the coordination number of the central metal atom. Complexes of metals
in low spin d7, d8, or d10configurations generally undergo this type of NOTES
reaction and in the process of enhancing their coordination number, the
central metal tends to attain the stable closed-shell configuration
corresponding to 18 valence electrons.
Coordinative unsaturated state of the central transition metal appears to
facilitate an 'oxad' type of reaction. For example, in the following
reaction, iridium (I) changes from 4-coordinate 16-electron to 18-electron
iridium (III):
X Oxidative Addition
M + M
Reductive elimination
Y
Y
IrCl(CO)(PPh3)2 + CH3I Ir(CH3) (CI)(I)(CO)(PPh3)2
Similarly, in the following reaction, 5-coordinate 18-electron

ruthenium(0) is converted into 6-coordinate 18-electron ruthenium (II),
accompanied by the loss of a CO molecule:
Ru(CO)3(PPh3)2 + CH3I Ru(CH3)(I)(CO)2(PPh3)2 + CO
To facilitate oxidative addition type of reactions, the metals should

preferably by in low oxidation state. Unlike the main group metals (e.g.
the formation of Grignard reagents from metallic magnesium and alkyl
halides), the transition metals themselves are not generally reactive
enough under ambient conditions and have to be in low oxidation state in
the presence of coordinated ligands.
The oxidative addition reactions have assumed special importance in
catalytic processes and this is generally the initiating step in a catalytic
process and involves the formation of bonding of some kind (,  other
delocalized type) between the transition metal and the organic/inorganic
substrate (through oxidative addition or coordination); this is generally a
key step in the catalytic or / and stoichiometric process, e.g.:
141
H
Catalysis Involving
Ph3P Cl PPh3
Organometallics
+ H2 Ph3P Rh + PPH3
Rh
PPh3 H
Ph3P Cl
NOTES
OC
CO
CO OHC CO
OC Mn + CH3Br Mn +Br
CO CO
CO OC CO
The oxidative addition/ coordination reaction of a ligand is generally

facilitated by the availability of vacant coordination site (s) on a metal
complex in solution (homogeneous catalysis) or a metal surface
(heterogeneous catalysis). The coordinative unsaturation may also arise
from the dissociation of loosely held solvent molecules, giving rise to
potentially vacant site(s). For example, a square planar d 8 (4-coordinate)
complex such as RhCl(PPh3)3 (known as Wilkinson's catalyst) is
coordinatively unsaturated and is one of the most active and versatile
catalysts known so far. In this connection, it may be noted that
coordinative unsaturation is generally guided by the 18-electron rule (or
effective atomic number rule).
In view of the extensive applicability of oxidative addition reactions in
catalysis, some of their essential features are indicated as follows:
(A) Low Oxidation State of the Metal
As oxidative addition reaction can be treated as a process undergoing loss
of electrons from the electron rich metal centres, the same should be
facilitated by the metal atom in the complex being in the lower oxidation
state; in fact, any change in the metal complex which enhances the
electron density at the central metal leads to an increase in reactivity.
Although theoretically metal atoms in metallic (or zero oxidation) state
could be expected to be better precursors for such reactions, yet these are
of only very limited applicability on energetic grounds. However, the
development of metal vapour and reactive metal production techniques
have added new dimensions in this particular area.
(B) Coordinative Unsaturation
The oxidative addition reactions are generally accompanied by an
increase in the coordination number of the central metal atom. It is,
therefore, expected that organometallic precursors should be
coordinatively unsaturated, e.g. IrCl(CO)(PPh3)2; (RhCl(PPh3)3, etc. The
coordinative unsaturation can be achieved either (i) by the generation of a
142
vacant coordination site or (ii) by the ability of a complex to exit in
different coordination numbers.
Catalysis Involving
Organometallics
(C) Nature of the Metal
There are many indications that the lighter metals in a given sub-group
are less basic or nucleophilic than the heavier elements. For example,
while the complex IrCI(CO)(PPh3)2 (Vaska's compound) reacts
NOTES
completely and irreversibly with CH3I:
Basic reaction:
X X
LnM + LnM
Y Y
The new M-X and M-Y bonds are formed using:

• the electron pair of the X-Y bond
• one metal-centered lone pair
The metal goes up in oxidation state (+2)
X-Y formally gets reduced to X-, Y-
Common for transition metals, rare for main-group metals
As the name implies reductive elimination involves the
elimination or expulsion of a molecule from a transition metal complex.
In the process of this elimination, the metal center is reduced by two
electrons.
In the simplest example below the metal goes from the x+2 to the x
oxidation state and a coordinatively unsaturated metal center is obtained.
In Equation 2 we see a case of a binuclear reductive elimination
reaction:
Reductive elimination is formally the microscopic reverse of oxidative

addition, and it is not surprising that a series of reactions involving an
oxidative addition, a rearrangement and then a reductive elimination
form the basis for a variety of industrially important catalytic cycles.
Factors which facilitate reductive elimination
 a high formal positive charge on the metal,
 the presence of bulky groups on the metal, and
 an electronically stable organic product.
 Cis orientation of the groups taking part in reductive elimination
is a MUST Almost the exact reverse of Oxidative Addition
143
11.4 Hydrogenation
Catalysis Involving The addition of hydrogen gas to ethylene to from an alkene is
Organometallics thermodynamically favourable, but it does not takes place at room
temperature and pressure.
H2C = CH2 + H2 CH3 – CH3
NOTES  Ho = -136 KJ mol-1
 Ho = -101 KJ mol-1
However this reaction is heterogeneously catalysed by metallic
Ni, Cu, Pd or Pt, the reaction is fast and complete.
The first effective homogeneous catalyst discovered for

hydrogenation of a alkenes was the square – planar 16 – electron d8
complex, chlorotris (triphenylphosphine) Rhodium (I) [(Ph3P)3 RhI Cl]
which is known as Wilkinsons catalyst. In the catalyst [(Ph3P)3 RhI Cl]
Electronic configuration = Rh I 4d7 5s1

Rh = 8e-
4 Ligands = 8e-
 = 16e- So coordinatively unsaturated.
Since  = 16 which has two electrons short of 18 electrons and
undergo oxidative addition and reductive elimination. So this complex
becomes 5 coordinative through a simple addition of ligand or 6
coordinate through addition combined with oxidation.
In either case it achieves 18e - valance shell configuration
Wilkinson‘s catalyst: The first example of an effective and rapid
homogeneous catalyst for hydrogenation of alkenes, active at room
temperature and atmospheric pressure.
Wilkinson's catalyst is catalyst for hydrogenation of alkenes. Square
planar 16 electron d8 complex (Ph3P)3RhCl.
Ph3P PPh3
RhI
Ph3P Cl
18 VE +H2
S = Solvent
+S -PPh3
S PPh3
R RhI +H2
Reductive
Elimination Ph3P Cl Oxidative H
16 VE addition H PPh3
RhIII
R Ph3P Cl
H H PPh3
PPh3 H PPh3
18 VE
RhIII RhIII +S
Ph3P Cl Ph3P Cl -PPh3
S
Migratory insertion of H R
18 VE 18 VE
Rate determining step
H
H PPh3
RhIII144 R
Self-Instructional Material Ph3P Cl
R
18 VE
Mechanism
 Wilkinson's catalyst is catalyzes the hydrogenation of alkenes. Catalysis Involving
Organometallics
 Mechanism involves the initial dissociation of one or two
triphenylphosphine ligands to give 14 or 12-electron complexes,
respectively. In solution one of the phosphine ligands dissociates,
leavings (Ph3P)2RhCl the reaction can be represented as follows
NOTES
(L = Ph3P, S – Solvent). Solvent must be an electron donar ie.,
Lewis base.
 Followed by oxidative addition of H2 to the metal. The
(Ph3P)2RhCl molecule, possibly solvated undergoes oxidative
addition of a H2 molecule.
 An alkene gets coordinated to the Rh metal atom displacing the
solvent.
 The hydride ion (H-) migrates from the metal to a carbon in the
coordinated alkene to form an alkyl group. This is often called an
alkene insertion reaction.
 The solvent reenters and occupy the vacant site.
 Finally reductive elimination of ethylene and regeneration of
catalyst takes place.
 The (Ph3P)RhCl formed in the dissociation step is tricoordinate, a
very reactive complex and has not as yet isolated, but the closely
related [Ph3P)3 Rh]+, which could form from the dissociation of a
chloride ion from Wilkinson catalyst has been studied and found
to have T – Shaped structure than triangular (3 – coordinate).
 The reaction involving a catalyst can always be represented by a
closed loop. The reaction 1 to 6 can be combined into a
continuous cycle (closed loop) called ‗TOLMAN CATALYTIC
LOOP‘ in which various catalytic species formed in the main
body of the loop the reactants and the products formed leaving at
appropriate loop.
 Other applications of Wilkinson‘s catalyst include: catalytic
hydroboration of alkenes and the selective 1,4-reduction of α, β-
unsaturated carbonyl compounds in concert with triethylsilane.
The rates of hydrogenations decrease with increase in the alkyl group

substitution on double bond mirroring their relative binding affinities to
the metal center. It is also partly due to steric factors.
R R R R R
R
R R R R R R R R
There is minimal scrambling of H/D in the product, when an equimolar

mixture of H2 and D2 are used
145
Catalysis Involving
Organometallics
Wilkinson's catalyst can be used to achieve selective hydrogenations.

• Less substituted and sterically less hindered double bonds are
NOTES
selectively hydrogenated.
• Exocyclic double bonds are selectively hydrogenated over
endocyclic double bonds.
Cis alkenes are reduced rapidly than trans alkenes.
Isolated double bonds are rapidly hydrogenated over conjugated dienes.
Terminal alkynes are hydrogenated more rapidly than terminal alkenes.

The selectivity can be enhanced by using acidic alcoholic co-solvents.
Functional groups like C=O, C=N, NO2, Aryl, CO2R etc., are unaffected.
The compatibility of Wilkinson's catalyst with polar multiple bonds
indicates the metal hydride bond is primarily covalent in character.
146
Catalysis Involving
Organometallics
NOTES
The reaction of an alkene with CO and H2 catalysed by Co or Rh
salts to form an aldehyde containing one more carbon atom than original
alkene is called ‗Hydroformylation‘ or ‗Oxo process‘.
The name hydroformylation arises from the fact that the H atom
and formyl group are added across a double bond. The net result of the
process is extension of carbon chain by one and introduction of the
oxygen to the molecule. Main industrial application is in the production
of butanal from propene. Further the products were generally mixtures of
linear and branched-chain isomers in roughly 3 : I ratio. The formation
of these is directed by anti-Markovnikov and Markovnikov additions
respectively.
cat O
R + CO + H2 + R
R O
n iso
A pre equilibrium is established in which CO2(CO)8 combines with H2 at

high pressure to yield the known tetra carbonyl hydride cobalt complex
HCo(CO)4.
[Co2(CO)8] + H2 2[HCo(CO)4] -
b) This complex loses CO to produce coordinately unsaturated complex

H Co (CO)3
[HCo(CO)4] [HCo(CO)3] + CO
c) An alkene coordinates to HCo(CO)3 producing 18e- complex.
CH2
[HCo(CO)4] + CH2=CHR H(CO)3Co
CHR
d) This 18 electron complex undergo migratory insertions of the olefin

into Co – H bond thereby creating another 16 electron complex (acyl
complex) and another.
147
CH2
H(CO)3Co (CO)3CoCH2CH2R
Catalysis Involving
Organometallics CHR
e) A CO of RCH2CH2Co(CO)4 migrates to a position between the

CO atom and alkyl group. This is the critical step in the formation of
NOTES aldehyde.
CO
(CO)3CoCH2CH2 R (CO)4 CoCH2CH2R
f) Reaction with either H2 or [HCo(CO)4] releases the aldehyde and

regenerates the catalytic Co complex.
H
O
(CO)3-Co-C-CH2CH2R
O
H
(CO)3CoC-CH2CH2R + H2
H2 H2
H C C C R + HCo(CO)3
O
This process may be carried out so that the aldehyde products are
reduced to give alcohol such as 1 – butanol or higher alcohols.
148
Prior to 1970, acetic acid was made using cobalt catalysts (BASF
process) In 1970 Monsanto commercialized a rhodium carbonyl iodide
catalyst that is commonly called the Monsanto Acetic Acid Process. The Catalysis Involving
Monsanto acetic acid process is the major commercial production method Organometallics
for acetic acid. Methanol, which can be generated from synthesis gas
("syn gas", a CO/H2 mixture), is reacted with carbon monoxide in the
presence of a catalyst to afford acetic acid. In essence, the reaction can be
NOTES
thought of as the insertion of carbon monoxide into the C-O bond of
methanol, i.e. the carbonylation of methanol.
The catalyst system has two components, iodide and rhodium.
Almost any source of Rh and I- will work in this reaction as they will be
converted to the actual catalyst, [Rh(CO)2I2]- under the reaction
conditions. Over 1,000,000 tons of acetic acid are produced every year
using the Monsanto process.
Cu/ZnO
CO/H2 CH3OH
180 C, 30 atm, CH3I, [RhI3. nH2O]
CH3OH + CO CH3COOH (99%)
[RhI3] + 3CO + H2O [RhI2(CO)2]- + CO2 + 2H+ + I-
The role of iodide is simply to promote the conversion of methanol to

methyl iodide, the species which then undergoes reaction with the Rh
metal catalyst
CH3OH + HI CH3I + H2O
The catalytic cycle: Once methyl iodide has been generated, the catalytic
cycle begins with the oxidative addition of methyl iodide to [Rh(CO)2I2]-.
Coordination and insertion of carbon monoxide leads an intermediate 18-
electron acyl complex which can then undergo reductive elimination to
yield acetyl iodide and regenerate our catalyst.
Notice that there are two catalytic cycles going in this reaction using
metal and iodide. The acetyl iodide produced in the lower cycle is then
hydrolyzed in the upper one to give acetic acid. This hydrolysis produces
HI which can then convert more methanol to iodide and continue the
cycle:
149
Catalysis Involving
Organometallics
In summary, the system is catalytic in both Rh and I-.

NOTES
CH3CO2H HI CH3OH
H2O
O
CO CH3I
H3C C OC
I RhI
I I
Reductive
Elimination Oxidative addition
CH3
CO
I CO
I COCH3 RhIII
III
Rh
OC I
OC I
I
I
CO
insertion
Benefits
 Uses a more efficient metal complex to synthesize a C-C bond
 Increased yield selectivity to > 99% based upon methanol
 Milder conditions needed for the synthesis (150-200 oC and 30-60
bar)
 Plant capacity: 500,000 tons annually
Challenges
 Rhodium: expensive and precipitates under low water
concentrations
 Large production of high boiling point by-products
 Replaced by an Iridium catalyst in the late 1990s by BP
Chemicals
The German chemist Karl Ziegler (1898-1973) discovered in 1953 that
when TiCl3(s) and AlEt 3 are combined together they produced an
150
extremely active heterogeneous catalyst for the polymerization of
ethylene at atmospheric pressure.
Catalysis Involving
Giulio Natta (1903-1979), an Italian chemist, extended the method to Organometallics
other olefins like propylene and developed variations of the Ziegler

catalyst based on his findings on the mechanism of the polymerization
reaction. The Ziegler-Natta catalyst family includes halides of titanium,
NOTES
chromium, vanadium, and zirconium, typically activated by alkyl
aluminum compounds. Ziegler and Natta received the Nobel Prize in
Chemistry for their work in 1963.
Polyolefins are the most important products of organometallic catalysis

(> 60 million Tons per year)
 Polyethylene (low, medium, high, ultrahigh density) used in
packaging, containers, toys, and house ware items, wire
insulators, bags, pipes.
 Polypropylene (food and beverage containers, medical tubing,
bumpers, foot ware, thermal insulation, mats)
Ziegler-Natta process for polymerization of alkenes, it would be
appropriate to point out that unsymmetrical alkenes can lead to different
types of arrangements in the polymer. Catalysed polymerization of
ethylene (ethene) produces a stereoregular polyethylene (polythene)
Proplyene, on the other hand, may form two stereoregular (either
isototactic or syndiotacitc) or a non-regular atactic povmer.
H2C CH2
isotactic
H2C C CH3 syndiotactic

H
atactic
 Isotactic polymer: In this all methyl groups lie on the same side of
the chain, which teds to adopt a helical shape so that the methyl
groups do not sterically interfere with one another.
151
 Syndiotactic polymer: In this, there is a regular alternation of
Catalysis Involving
methyl groups along the chain.
Organometallics  Atactic polymer: In this, there is no regularity in the configuration
of methyl groups along the chain.
Zeigler – Natta Catalyst – TiCl4 C2H5. It is a Lewis acid. Accepts a pair
of electron to form coordinate bond. It is coordinatively unsaturated.
NOTES
Mechanism
TiCl4 + AlEt3
-AlEt2Cl
Et
Cl Cl
Ti
Cl
migration Cl
Active species
R may be C2H5/C4H9
H2C Et Et
Cl Cl
Ti Cl Cl
CH2 Ti
Cl
Cl Cl
Cl
Active species
R may be C2H5/C4H9 complex
Et CH2
Cl Cl
Ti CH2
Cl
Cl
Transition state
 The Al(C2H5)3 alkylates the Ti – atom on the surface of the solid.
TiCl4 + Al(C2H5)3 TiCl4 C2H5

152
 An ethene molecule coordinates to the neighboring vacant site.
 The coordinated alkyl group undergoes a migratory insertion Catalysis Involving
Organometallics
reaction. This is the propagation step for the polymerization.
 This migration opens up another neighbouring vacancy and so the
next alkene molecule can coordinate and so the reaction can
continue and the polymer chain can grow. This vacant site can be NOTES
occupied by another ethene molecule and the insertion process is
repeated and steps (2) and (3) continued until a chain termination
process occurs by the severing of the titanium-alkyl bond
Et
Et
H2C CH2
H2C CH2
Cl Cl Cl Cl
Ti + Ti
Cl Cl
Cl Cl
complex
 The release of polymer from metal atom occur by  - hydrogen

elimination and the chain is terminated.
 The stereoregularity or polypropylene was assumed to arise due
to the nature of sterically controlled directing sites on the TiCl3
lattice.
Applications
The Ziegler-Natta catalyst polymerisation is a beneficial and versatile
reaction for producing polymers. Some of the most popular applications
of this catalyst are;
They are used for the production of High and Low-Density Polyethylene.
Production of thermoplastic polyolefins, polybutylene, crystalline
polypropylene and carbon nanotubes nanocomposites.
Limitation of Ziegler-Natta Catalyst
Ziegler-Natta polymerisation has some limitations as it does not work for
some monomers. Products like poly(vinyl chloride) cannot be generated
by Ziegler-Natta polymerisation. Acrylates are also another example.
11. 8 Isomerisation
Valence isomerisation of strained hydrocarbons.
A number of complexes, notably of RhI, Pdo and Nio will induce valence
isomerization of strained hydrocarbons. A typical example is the
interconversion of norbornadiene and quadricyclane.
153
The reaction proceeds readily with metal ions such as Fe I or CuI in the
gas phase. The forward reaction is catalyzed for example, by PdCl2
Catalysis Involving
Organometallics (norbornadiene) while the norbornadiene  quadricyclane
III
photoismerization is sensitized by an Ir ortho – metallated complex,
[(bipy)2Ir(2, 2ˈ– bipyrid – – yˈ–C3, Nˈ)]2+
NOTES Most reactions of this type are considered to proceed by oxidative

addition and cleavage of the C – C bond. For cyclopropane the reaction
with [RhCl(CO)2]2 gives an isolable intermediate.
O
CO Cl
2 + [RhCl(CO)2]2 Rh Rh
Cl CO
O
A few other intermediate have been isolated with non – carbonyl

complexes eg RhCl(PPh3)3, the reaction is through to proceed as
+ LnRhI
-RhILn
Cubane RhIII
Ln syntricyclooctadiene
The Ag+ ion also catalyses such isomerization, but these proceed by
electrophilic cleavage of C – C bonds followed by carbonium ion
rearrangements.
Ag + Ag
Cubane Cuneane
11.9 check your progress questions
1. Explain Turnover Frequency.

2. Describe Catalytic Cycles
3. What is meant by reductive elimination reaction?
154
4. Give molecular structure of Wilkinsons Catalyst
5. What is Hydroformylation reaction?
6. Describe Ziegler-Natta process Catalysis Involving
Organometallics
 A catalyst‘s turnover frequency number, or turnover number per
time unit, characterizes its level of activity. So the TOF is the
total number of moles transformed into the desired product by NOTES
one mole of active site per hour. Larger the TOF, the more active
the catalyst. TOF = TON/hour.
 The essence of catalysis is a cycle of reactions that consumes the
reactants, forms products and regenerates the catalytic species.
The catalytic cycle operates in the principle of microscopic
reversibility. i.e., If a certain series of steps constitutes the
mechanism of a forward reaction, the mechanism of the reverse
reaction is given by the same steps traversed backwards.
 reductive elimination involves the elimination or expulsion of a
molecule from a transition metal complex.
 Square planar 16 electron d8 complex (Ph3P)3RhCl.
 The reaction of an alkene with CO and H2 catalysed by Co or Rh
salts to form an aldehyde containing one more carbon atom than
original alkene is called ‗Hydroformylation‘ or ‗Oxo process‘.
 Ziegler-Natta process for polymerization of alkenes, it would be
appropriate to point out that unsymmetrical alkenes can lead to
different types of arrangements in the polymer.
11.11 Summary
 The essence of catalysis is a cycle of reactions that consumes the
reactants, forms products and regenerates the catalytic species.
 Catalytic efficiency of a catalyst is expressed in turn over number
(N).
 Oxidative addition (or oxad) reaction which are useful for
establishment of new transition metal-carbon -bonds involve the
oxidation (i.e., increase in the formal oxidation number),
accompanied by an increase in the coordination number of the
central metal atom
 The first example of an effective and rapid homogeneous catalyst
for hydrogenation of alkenes, active at room temperature and
atmospheric pressure.
 During Oxo process the products were generally mixtures of
linear and branched-chain isomers in roughly 3 : I ratio. The
formation of these is directed by anti-Markovnikov and
Markovnikov additions respectively.
155
11.12 Keywords
Catalysis Involving  Oxo process: The reaction of an alkene with CO and H2
Organometallics catalysed by Co or Rh salts to form an aldehyde containing one
more carbon atom than original alkene is called ‗Oxo process‘.
 Monsanto Acetic Acid Process: Monsanto commercialized a

NOTES rhodium carbonyl iodide catalyst that is commonly called the
Monsanto Acetic Acid Process.
 Zeigler – Natta Catalyst – TiCl4 C2H5. It is a Lewis acid.
Accepts a pair of electron to form coordinate bond. It is
coordinatively unsaturated.
 isomerization: RhI, Pdo and Nio complexes will induce valence
isomerization of strained hydrocarbons.
 Isotactic polymer: In this all methyl groups lie on the same side
of the chain, which tends to adopt a helical shape so that the
methyl groups do not sterically interfere with one another.
1. Write a note on hydrogenation of alkenes

2. Discuss the mechanism of Zeigler-Natta Catalyst
3. Write the advantages of Monsanto process.
4. What is oxidative addition?
5. What is TON?
7. Modern aspects of Inorganic chemistry, H.J. Emelius and Sharpe,

Universal book Stall, New Delhi, 1989.
8. Inorganic Chemistry- Principles of structure and reactivity, J.E.
Huheey, E.A. Keiter and R.L. Keiter, 4 th edition, Pearson-Education,
2002.
9. Advanced Inorganic Chemistry - F.A. Cotton and G. Wilkinson,
Wiley Eastern, 5thedition, 1998.
10. Inorganic Chemistry, D. F. Shriver and P. W. Atkins, Oxford U.K.,
1999.
11. Chemistry & Chemical Reactivity, John C. Kotz, Paul M.
Treichel, John Townsend, 8thed., USA, 2012.
12. Inorganic Chemistry,. G. S.Sodhi; IstEdition, VB (P) Ltd, 2006.
156
UNIT-12 METALLOPORPHYRINS AND
METALLOENZYMES Metalloporphyrins and
Metalloenzymes
Structure
12.0 Introduction
12.1 Objectives
12.2 Chlorophyll NOTES
12.3 Structure and function of Hemoglobin (Hb) and
myoglobin (Mb)
12.3.3 Cooperativity
12.4 Cytochromes
12.5 Enzymes
12.5.2 Inhibition
12.6 Vitamin B12 and B12 coenzymes
12.6.2 Function
12.7.1 Structure
12.8.1 Structure
12.10 Summary
12.11 Keywords
12.0 Introduction
A cofactor is a non-protein chemical compound that is bound to a
protein and is required for the protein's biological activity. These proteins
are commonly enzymes. Cofactors are either organic or inorganic. They
can also be classified depending on how tightly they bind to an enzyme,
with loosely-bound or protein-free cofactors termed coenzymes and
tightly-bound cofactors termed prosthetic groups. Over 25% of all
enzymes contain tightly bound metal ions or require them for activity.
1. Metalloenzymes - contain definite quantity of functional metal ion that
is retainedthroughout purification. Metal ions, most commonly transition
metals, are Fe2+, Fe3+,Cu2+, Zn2+, Mn+, or Co3+.
157
2. Metal-activated enzymes - loosely bind metal ions from solution, and
require them forcatalysis. Usually the presence of the alkali and alkaline
Metalloporphyrins and
Metalloenzymes earth metal ions is required:Na+, K+, Mg2+, or Ca2+.
The distinction between metalloenzymes and metal-activated enzymes
thus restson the affinity of a particular enzyme for its metal ion.The
mechanism whereby metal ions perform their functions appear to be
NOTES similar inmetalloenzymes and metal-activated enzymes. The flowchart
will explain the metallobiomoleucles.
Metallobiomolecules
Transprot and storage protein Enzymes Non-proteins
electron carrier metal storage Metal transport Photoredox

carrier and structural O2 binding and structrual
Cytochromes (Fe) Siderophores(Fe) Chlorophyll (Mg)

Myoglobin (Fe) Photosystem II (Mn, Mg)
Iron-sulfur (Fe)proteins Hemoglobin (Fe) Skeletal (Ca, Si)
Ferritin (Fe)
Transferrin (Fe)
Hydrolases Oxido-reductases Isomerases and synthetases
Carboxypeptidases (Zn) Oxidases (Fe, Cu, Mo) Vitamin B12

Aminopeptidases (Mg, Mn) Aminopeptidases (Mg, Mn) ) Dehydrogenases (Fe,
Phosphatases (Mg, Zn, Cu) Phosphatases (Mg, Zn, Cu) (reductases) Cu, Mo) coenzymes (Co
Hydroxylases (Fe, Cu, Mo)
Oxygenases (Fe)
Superoxide dismutase (Cu, Zn, Mn)
Nitrogenase (Fe, Mo)
Hydrogenases (Fe)
Porphyrins are tetradentate ligands which have the characteristic property

of complexing with metal ions such as Fe2+, Fe3+, Zn2+, Cu2+ and Co3+.
The co-ordination compounds thus formed are metal chelates called
metalloporphyrins. Metalloporphyrins are coloured compounds (organic
pigments) found in living organisms. The iron porphyrin which
constitutes the haem part of haemoglobin in a well known example of
Metalloporphyrin.
12.1 OBJECTIVES
 Understand the structure and function of hemoglobin
 Explain the enzyme action
 Understand the mechanisms behind B12 and B12 coenzymes.
Self-Instructional Material  Learn about the Copper containing oxidases
 Describe about Chlorophyll-
158
12.2 Chlorophyll
Chlorophyll is the molecule that absorbs sunlight and uses its energy to
synthesise carbohydrates from CO2 and water. This process is known as Metalloenzymes
photosynthesis and is the basis for sustaining the life processes of all
plants. Since animals and humans obtain their food supply by eating
plants, photosynthesis can be said to be the source of our life
also.Chlorophyll is the green colouring matter (pigment) of plant leaves. NOTES
Natural chlorophyll is a 3:1 mixture of chlorophyll – a and chlorophyll –

b. They differ only slightly, in the composition of a sidechain (in a it is -
CH3, in b it is CHO). Both of these two chlorophylls are very effective
photoreceptors because they contain a network of alternating single and
double bonds, and the orbitals can delocalise stabilising the structure.
Such delocalised polyenes have very strong absorption bands in the
visible regions of the spectrum, allowing the plant to absorb the energy
from sunlight. There is extensive conjugation of the porphyrin ring in
chlorophyll. This lowers the energy of the electronic transitions and shifts
the absorption maximum into the region of visible light. Conjugation
also helps to make the ring rigid, and thus less energy is wasted in
internal thermal degradation (via, molecular vibrations).
The chlorophyll ring system is a porphyrin in which a double bond in one
of the pyrrole rings has been reduced.
 Chlorophylls are numerous in types, but all are defined by the
presence of a fifth ring beyond the four pyrrole-like rings.
 Most chlorophylls are classified as chlorins, which are reduced
relatives to porphyrins (found in hemoglobin).
 The chlorin ring can have various side chains, usually including a
long phytol chain.
 It is a magnesium porphyrin complex in which one of the pyrroles
is partically reduced.
 A cyclopentanone ring is fused to the pyrrole ring C.
 Both the acid chains in chlorophyll are esterified – one is the
methyl ester (COOMe) and the other is an ester of phytol
(C20H39OH).
159
R
Metalloenzymes
H3C
N N
NOTES R = CH3; Chlorophyll a
Mg R = CHO; Chlorophyll b
N N
H3C
CH3
H3COOC O
O CH3
CH3 CH3
O CH3 CH3

It is capable of channelling the energy of sunlight into chemical energy
through the process of photosynthesis. In this process the energy
absorbed by chlorophyll transforms carbon dioxide and water into
carbohydrates and oxygen
h
6CO2 +6 H2O Chl C6H12O6 + 6 O2
The chemical energy stored by photosynthesis in carbohydrates drives
biochemical reactions in nearly all living organisms.
In the photosynthetic reaction electrons are transferred from water to
carbon dioxide, i.e carbon dioxide is reduced by water. Chlorophyll
assists this transfer as when chlorophyll absorbs light energy, an electron
in chlorophyll is excited from a lower energy state to a higher energy
state. In this higher energy state, this electron is more readily transferred
to another molecule. This starts a chain of electron-transfer steps, which
ends with an electron being transferred to carbon dioxide. Meanwhile,
the chlorophyll which gave up an electron can accept an electron from
another molecule. This is the end of a process which starts with the
removal of an electron from water. Thus, chlorophyll is at the centre of
the photosynthetic oxidation-reduction reaction between carbon dioxide
and water.
160
Photosynthesis is a light driven oxidation – reduction process. Water is Metalloporphyrins and
oxidized to O2 by a reaction in the presence of light. This is called light Metalloenzymes
reaction. CO2 is reduced to form glucose in a light independent reaction
called dark reaction. In the light reaction causes oxidation of H2O to
release O2 and generation of ATP and NADPH (reductant) by a process
NOTES
called photophosphorylation.
h
6CO2 +6 H2O Chl C6H12O6 + 6 O2
Light reaction
Chlorophyll absorbs light and gets excited. The excited
chlorophyll molecule expells an electron which is rapidly transferred to
electron carriers like ferridoxin and used to reduce NADP. The
chlorophyll comes to the ground state by receiving an electron released
by the decomposition of water by a Mn-containing complex via
cytochromes.The electron translocation leads to ATP synthesis.
h * *
Chl Chl Chl + e-
NADP
Fd + e- Fd + e- Fd + NADPH
h
Dark reaction
CO2 is reduced to hexose in the dark reaction which utilizes the
NADPH and ATP generated by the light reaction (calvin cycle). Totally
three ATP and two NADPH molecules are consumed by one molecule of
CO2.
6CO2 + 18 ATP + 12 NADPH C6H12O6 + 18ADP + 18 Pi + 12 NADP
12.3Structure and function of Hemoglobin (Hb) and myoglobin (Mb)
The function of both Hb and Mb is to bind oxygen, but their
physiological roles are very different. Hemoglobin picks up oxygen in
the lungs and carries it to tissues.Haemoglobin is an effective buffer for
blood. The buffering capacity is due to the presence of ionisable groups
in the imidazole side chain of histidine residues. Cellular oxygen is
stored by Myoglobin, until it is required for metabolic action.
Hemoglobin has an additional function of carrying CO2 back to the
lungs.Hb has the molecular weight 64,500 daltons. Each Hb molecule has
four hemegroups bound to the globin on its surface. In each heme unit of
Hb the four square-planar coordination positions of Fe(II) are being
occupied by the four nitrogens of theprotoporphyrin ring the fifth
coordination position of Fe(II) is occupied by the imidazolenitrogen of
histidine residue of the protein chain i.e. globin chain, and the sixth
161
coordination position of Fe(II) is occupied by O 2 on oxygenation.In a
Metalloporphyrins and haem – proteins made of two parts . 1. Globin (96%) – protein part
Metalloenzymes andHaem (4%) – prosthetic group.
Hb consists of a tetrahedral arrangement of four heme groups
each surrounded by its polypeptide (globin) chain. Normal adults have
NOTES two α and two β type subunits and Hb can accordingly be represented as
α2β2. The α and β forms are distinguished by their different amino-acid
sequences α-141, β-146.
Myoglobin (Mb) (MW 17, 800) is a monomer having only one molecule
of heme. The peptide chains in Hb and Mb have extensive helical
structure. There are 7 helical segments in the α chains and 8 in the β and
myoglobin forms. These are linked by short non-helical segments.In free
heme molecule there are two coordination positions above and below the
plane of the porphyrin molecule. These two positions are occupied by
water molecules.
HO OH
H3C CH3
N N
Fe
N N
CH3
CH3
Heme
{Fe-protoporphyrin IX}
The iron (II) ion in heme is very sensitive to oxygen and it undergoes
combinationwith it readily to form a labile Fe (II)-O2 complex (Oxy-
heme) which changes into the Fe(III) protopophyrin called hematin or
hemin. Hence free heme is not favored for oxygentransport. Hence an
important function of the globin in hemoglobin, apart from the actionas a
carrier of heme, has been found to stabilize the heme-O2 complex so that
oxidationof iron of heme does not take place and it can act as an effective
carrier of oxygen. As aprotein chain is folded around the heme group, the
position of the protein chain reducesthe access of water to Fe2+ and at the
same time provides a hydrophobic surrounding.Thus the steric and
chemical control permits the access of oxygen molecule but does
162
notpermit the simultaneous presence of oxygen and one or more
molecules of water whichappears to be necessary for oxidation of Fe2+ to
Fe3+.The iron in Mb and Hb in +2 oxidation state. The oxidized forms Metalloporphyrins and
containing iron(III) called met Mb and met Hb, will not bind oxygen. Metalloenzymes
NOTES
Typical curves of oxygenation vs. oxygen pressure (P O2) under

physiologicalcondition for Hb and Mb. Curves for oxygenation of Mb is
hyperbolic while that of Hb issigmoidal in nature. It is the cooperativity
of the four-heme groups that produces twotypes of the curves shown in
figure. Figure shows that Hb is about as good an O2 binderas Mb at high
O2 pressure. It is much poorer at the lower pressures prevailing in
muscleand hence passes its oxygen on to Mb as required. Moreover, the
need for O2 will begreatest in tissues where O2 is consumed followed by
production of CO2. The CO2 lowersthe pH, thus causing the Hb to release
even more oxygen to Mb. The pH-sensitivity(called the Bohr effect) as
well as the progressive increase of O2 binding constants in Hbare due to
the interaction between the subunits; Mb behaves more simply because
itconsists of only one unit. It is clear that each of the two is essential in
the completeoxygen transport process.The oxygenation curve of Mb
reflects a simple equilibrium
Mb + O2 MbO2
[MbO2]
KI = 1
[Mb] [O2]
[Mb] total = [Mb] + [MbO2]
[Mb] total = [Mb] + KI[Mb][O2] from equation 1 substituting the value of [MbO2]
163
[Mb] total = [Mb] [1 + KI[O2]]
Substituting the value of [Mb] total in equaiton - 2
[Mb] KI[O]2
[
Metalloporphyrins and [Mb] [1 + KI[O]2]
Metalloenzymes
Value of [MbO2] sustituted from equaion 1

NOTES
KI[O]2
[ 3
[1 + KI[O]2]
1
1 -  4
[1 + KI[O]2]
Dividing equaion 3 by equaion 4
[
1- = KI[O2]
This equaitonis for Mb
Oxygenation curve of Hb may be approximated as

[
1- = KI[O2]n with n ~ 3
This equation is known as Hill equation and the exponent, n is
called the Hillconstant. In contrast to the hyperbolic curve obtained from
the data for the monomericheme (myoglobin), the data obtained by Hb
shows ―Sigmoidal‖ behavior, indicative ofinteraction between the
subunits. The data obtained from Hb between 10 and 90%oxygenation
can be fitted to the Hill equation to give values of n ~ 3 for normal
Hb.The form of oxygenation curve and that the fact if fits n>1 indicate
that there iscooperative interaction between the subunits. The addition of
oxygen to a subunit affectsthe oxygen affinities of other subunits, this is
an example of Allosteric effect (Entaticeffect) literally means ―a
stretched state or state of being under tension‖. n<4 indicatesthat the
cooperative interaction between heme units is rather moderate.
Hb binds with O2 to form oxyhaemoglobin (an unstable
complex) at high partial pressure (100 mm of Hg), in the lungs.
Hb + O2 HbO2.
164
Since there are 4 haem units, fully saturated oxyhaemogoglobin (96%)
carries 4 O2 molecules.
The oxyhaemoglobin dissociates into deoxyhaemoglobin at a Metalloporphyrins and
Metalloenzymes
low partial pressure (45mm of Hg), which prevails in tissues.
HbO2 Hb + O2.
The oxygen thus released is bound by Myoglobin, as it has higher affinity
NOTES
for O2 at low partial pressures.
Hb may be viewed as tetrameric of Mb. It has four heme groups
bound to fourprotein chains. The differences between Hb and Mb in their
behavior towards oxygen isrelated to the structure and movements of the
four chains. It is found that, uponoxygenation of Hb, two of the heme
groups move about 1 Ao towards each other whiletwo other separate by
about 7Ao. These movements seem responsible for the cooperativeeffect
observed. According to Perutz, changes in the coordination of the iron
play a crucial role. DeoxyHb contains iron(II) in a high spin state, with
two electrons occupying eg orbitals, thebonding radius of the iron is so
large (0.78 Ao) that it can not fit into the plane of four Natoms of the
heme porphyrin. It therefore lies around 0.75 Ao out of the plane. The
iron isthus pentacoordinate with square pyramidal coordination provided
byfour porphyrinnitrogen atoms in the basal position and an imidazole
nitrogen atom from histidine in theapical position.When an oxygen
molecule is bound in the position opposite to this histidine, theiron atom
goes in to a low spin state, eg. orbitals are then empty and the radius of
the irondecreases (by 0.17 Ao) so much that it now fits in to the plane of
the porphyrin system.Thus the iron atom moves down when deoxy Hb
becomes oxygenated. Since it remainsattached to the side chain of
histidine this shift is transmitted to various parts of thesubunits, causing
particularly important movements of the entire helical section.
12.4 Cytochromes
Cytochromes are membrane-bound(i.e., inner mitochondrial
membrane) heme proteins containing heme groups and are primarily
responsible for the generation of ATP via electron transport and catalysis
by reduction or oxidation of their heme iron. In the process of oxidative
phosphorylation, a globular cytochrome c protein is involved in the
electron transfer from the membrane-bound complex III to complex IV.
It links the oxidation of substrates to the reduction of O2. Cytochromes
are found in all aerobic forms of life. They are small molecules with a
molecular weight 12,000). They operate by shuttling of the iron atom
between FeII and FeIII.They are found bound on the inner mitochondrial
membrane either as monomeric proteins (e.g., cytochrome c) or
as subunits of bigger enzymatic complexes that catalyze redox reactions.
165
These heme proteins are classified on the basis of the position of their
lowest energy absorption band in the reduced state, as
Metalloenzymes cytochromes a (605 nm), b (~565 nm), and c (550 nm).A view of the
structure of a typical cytochrome c, is shown below. The iron – porphyrin
unit is seen edge-locked in a pocket created by the folding of the peptide
chain. The iron atom is ligated on both sides of the porphyrin plane by
NOTES the CH2CH2SCH3 side chain of a methionine and a nitrogen atom of a
histidine. The rest of the pocket is lined by hydrophobic side chains and
only a small part of the rim of the porphyrin ring is at or near the exposed
surface of the molecule.
S(Cys) Protein
protein S(Cys) Protein
N N
N N CH3
H Fe S
methionine
N N residue of
protein
OH
HO O
O
The following figure shows that electrons originating with reduced
coenzyme Q (CoQ) are accepted by a cytochrome b and proceed through
a series of intermediate cytochromes, until at the end, four electrons are
delivered at an appropriate potential to carry out the reduction of O2 to
water. Reduced CoQ
Cytochrome b (Cyt b)
Cyt c1
Cyt c
O2
Cyt a + Cyt a3 + 4 H+
2H2O
166
The redox potentials of the intervening cytochromes gradually increase to
cover the gap stepwise between that for the oxidation of reuced CoQ and
that for reduction of dioxygen. Metalloporphyrins and
Metalloenzymes
To do this, the cytochromes have distinctive structures and
properties.
In cyt b, cyt c1 and cyt c the heme group is the same as that in NOTES
haemoglobin and myoglobin. In Cyt b, the haem is not covalently
attached to the protein, but is held only by ligation to the iron atom. In
cyt c1 and cyt c, the haem is covalently connected by thioether linkages
and the iron atom is coordinated by protein side chains.
Cytochromes a and cyt a3 exist together as a complex, sometimes
called cytochrome oxidase, and they contain a heme with several
different substituents on the periphery of the porphyrin ring. Cyt a 3 also
contains copper, which goes from CuII to CuI and thus transfers an
electron from the haem of Cyt a3 to the dioxygen molecule. In general,
the processes are outer-sphere reactions that can be accounted for by the
Marcus theory.
Cytochromes C seems to be one of the most ancient of
biomolecules, having evolved in essentially its present form, more than
1.5 billion years ago, even though it is present in all animals and plants,
including those that have appeared more recently. It has been found that
the cytochrome C of any eukaryotic species will reach with the
cytochrome oxidase of any other species, thus confirming that this
electron transfer chain has resisted evolutionary change for a very long
time.
12.5 Enzymes
• Enzymes are biologically active proteins that accelerate the
breakdown of food that is eaten.
• Enzymes are biological catalysts. They accelerate reactions, but
are not consumed or changed in reactions. They not only control
the rate of reactions, but can lower the activation energy for the
formation of one product rather than another.
• Enzymes are named by adding the suffix -ase to the name of the
substrate on which it acts. For example, Lipase enzyme is
substrate of Lipid, and Amylase enzyme is substrate of Amylum.
• Enzymes are highly specific in their action, and are capable of

bringing out only one or a small group of reactions. Thus,
specificity is an important criterion for an enzyme.
167
Metalloporphyrins and To illustrate the structure of an enzyme and its relation to
Metalloenzymes
function, consider carboxy peptidase A. This is a pancreatic enzyme,
which cleaves the carboxyl terminal amino acid from a peptide chain by
hydrolyzing the amide linkage.
NOTES H2O
……Pro-Leu-Glu-Phe …..Pro-Leu-Glu + Phenylalanine
Carboxy-peptidase A
The enzyme consists of a protein chain of 307 amino acid
residues plus one Zn2+ ion to give a molecular weight of about 34,600.
The molecule is roughly egg-shaped. There is a cleft on one side, that
contains Zn2+ ion, which is the active site. The metal is coordinated
tetrahedrally to two N atoms and an oxygen atom from three amino acids,
in the protein chain. The above example illustrates the basic key and lock
theory first proposed by Emil Fischer in which the enzyme and substrate
fit each other sterically. There is evidence that the enzyme also
encourages the reaction by placing a strain on the bond to be broken.
The substitution of a different metal into an enzyme provides a very
useful method for studying the immediate environment of the metal site.
12.5.2 Inhibition
Ligands that can coordinate to an active center in an enzyme and
prevent coordination by the substrate will tend to inhibit the action of that
enzyme. Carbonic anhydrase inhibitors are a class of pharmaceuticals
that suppress the activity of carbonic anhydrase. Their clinical use has
been established as anti-glaucoma agents, diuretics, antiepileptics, in the
management of mountain sickness, gastric and duodenal ulcers,
idiopathic intracranial hypertension, neurological disorders, or
osteoporosis.
1. An example is that of carbonic anhydrase which catalyses the
interconversion of CO2 and carbonates, i.e., that drives the hydration of
carbon dioxide and dehydration of bicarbonate. It is found in Parietal
Cells in Stomach, Pancreatic duct cells, Red blood cells and found in
ciliary process, cornea, iris, and retina. Like carboxypeptidase, carbonic
anhydrase has one zinc atom per molecule (with a molecular weight of
30,000) and coordinated to 3 histidine residues (His 94, His 96, His 119)
and a water molecule of hydroxide ion. The active site contains other
amino acids that may function through hydrogen bonding, proton transfer
Self-Instructional Material etc. The relative bonding power of Zn ion towards halide ions is
reversed in the enzyme (I ->Br->Cl->F-). This reversal maybe due to the
168
‗softening‘ effect on Zn by the apoenzyme. Also NO3-, CNO- and N3- are
bound with exceptional strength. This can be explained by the structure
of the enzyme to form a pocket about 450 pm long next to the Zn2+ ion, Metalloporphyrins and
Metalloenzymes
an additional positive center to stabilize ions of appropriate size.
Carbonic
anhydrase NOTES
CO2 + H2O HCO3- + H+
H2CO3
Mechanism of Action
The zinc atom is thought to be more acidic in carbonic anhydrase
than in carboxypeptidase A. The substitution of a third, neutral and less
basic histidine in place of the glutamate anion contributes to the greater
acidity.
This polarises an attached water molecule, perhaps to the point of
loss of a hydrogen ion to form a coordinated hydroxo group. The
mechanism of the reversible hydration of CO2 to carbonic acid, follows
the pathway given below.
Inhibitor binds to active site, blocking interactions of water bound to zinc
and inhibiting enzymatic activity. The water bound to the zinc ion is
broken down to proton and hydroxyl ion. Zinc (since positive) stabilizes
negatively charge hydroxyl so it can attack carbon dioxide.
CAH2 inhibitor helps block the enzyme shifts the fluid balance,
reducing the pressure. Inhibitors are mostly sulfanomides.
Acetazolamide, dorzolamide (All compounds are sulfonamides).
Inhibition of membrane-bound carbonic anhydrase (CA) in the cells of
proximal tubule which leads to blockade of the reaction H2CO3 = H2O +
CO2 that normally occurs in the proximal tubule lumen. Inhibition of
cytoplasmic CA in the cells of proximal tubule which leads to blockade
of the reaction: H2O + CO2 = H2CO3 that normally occurs in the
cytoplasm The final effect is a nearly complete abolition of NaHCO 3
reabsorption in the proximal tubule (but NaHCO3 reabsorption by
mechanisms independent from carbonic anhydrase still occur in other
parts of the nephron).
169
2. Inhibition may also be effected by metal ions. Coordination of the
apoenzyme to a heavier metal ion may destroy the enzymatic activity.
Metalloenzymes Metal ions such as Hg2Cl2 are poisonous. Hg2+ has a special affinity for
S and tends to form extremely stable complexes such as cysteine, and
methionine.
NOTES
The affinity of S and Hg are attributed for the poisonous effects of Hg in
biological system. Often these effects are reversed by addition of sulphur
– containing compounds such as cysteine or glutathionine. Another
sulphur donor, 2, 3 – dimercaptopropanol has proved to be extremely
useful as an antidote for Arsenic, Cadmium and Mercury poisoning.
3. Uric acid is the chief end product of purine metabolism in primates,
birds, lizards and snakes. Due to metabollic errors in humans, there is an
increase in uric acid levels and its deposition as crystals in joints. This
condition (gout) may be treated by the drug allopurinol, which is
oxidised by Xanthine oxidase to alloxanthine. However, alloxanthine
binds so tightly to the Mo, that the enzyme is inactivated, the catalytic
cycle is broken and uric acid formation is inhibited. The extra stability of
the alloxanthine complex may be a result of N-H…..H hydrogen bonding
by the N in the 8th position.
12.6 Vitamin B12 and B12coenzymes
Chemical structure of Vitamin B12

Vitamin B12 is the only known essential biomolecule with a stable metal-
carbon bond, that is, it is an organometallic compound. Vitamin B12 is the
only, metal-containing vitamin –it is also a water-soluble vitamin that is
stored in the liver andmust come from the diet.Vitamin B12 (cobalamin)
only synthesized bybacteria and micro-organisms.
 The core of the molecule is a corrin ring with various attached
side groups.
 The ring consists of 4 pyrrole subunits, joined on opposite sides
by a C-CH3 methylene link, on one side by a C-H methylene link,
and with the two of the pyrroles joined directly. It is thus like a
porphyrin, but with one of the bridging methylene groups
removed.
 The nitrogen of each pyrolle is coordinated to the central cobalt
atom.
 The cobalt can link to: 1. a methyl group - as in methylcobalamin.
2. 5'-deoxyadenosine at the the 5' positon - as in
170
adenosylcobalamin (coenzyme B12). 3. a cyanide group - as in
Vitamin B12.
 The center-piece in the structure is of course the cobalt(III), the Metalloporphyrins and
Metalloenzymes
octahedral coordination to five nitrogens and a carbon is common
to all three cobalamins,
 The sixth ligand below the ring is a nitrogen of a 5,6-
dimethylbenzimidazole. The other nitrogen of the 5,6- NOTES
dimethylbenzimidazole is linked to a five-carbon sugar, which in
turn connects to a phosphate group, and back onto the corrin ring
via one of the seven amide groups attached to the periphery of the
corrin ring.
 The base ligand thus forms a 'strap' back onto the corrin ring. An
important aspect of the corrin ring, when compared to the
porphyrin, is the relative flexibility of the corrin system, the
corrin ring is also less flat when viewed from the side than is a
porphyrin ring.
 This adds up to some considerable differences between the
chemistry of a cobalt porphyrin and a cobalt corrin.
 In addition, the corrin only has a conjugated chain around part of
the ring system, whereas a porphyrin is delocalised around the
whole four pyrolle rings.
171
Metalloenzymes Vitamin B12 may be reduced by one electron (Vitamin B12r) or two electron
(vitamin B12s) to form the Co(II) and Co(I) complexes, respectively.
The latter is strongly nucleophilic and readily undergoes alkylation via
oxidative addition. III -
NOTES [B12 (CoI)] + CH3I [B12Co - CH3]+I
In biological systems the two – electron reduction may be accomplished by

NADH and flavin adenine dinucleotide (FAD). The methyl donor is N5-
methyltetrahydrofolate (CH3-THF). The Co (III) corrinoid (methyl
cobalamine) can then takepart in biomethylation reactions.
cobalamin
Vitamine B12 Methionine CH3
CH3 THF
THF methylcobalamin Homocysteine
Tetrahydrofolate
5-methyltetrahydrofolate transfer a vitamin B12 transfer a methyl group

methyl group to vitamine B12 to homocysteins to form methionine
12.6.2 Function
 Vitamin B12 is important for the normal functioning of the brain
and nervous system and for the formation of blood. It controls
the production of blood platelets and red and white blood cells.
 It is involved in the metabolism of every cell of the body,
especially affecting DNA synthesis and regulation but also fatty
acid synthesis and energy production. Both vitamin B12 and the
vitamin folate are essential for the production of DNA and RNA.
 Cyanocobalamin promotes normal growth and development;
treats pernicious anaemia. This is a disease caused by inability to
absorb vitamin B12 through the gut wall. It is due to the increase
in excretion of methylmalonic acid, as the body fails to convert it
to succinic acid.
 Vitamin B12 helps in the maintenance of the central nervous
system
 B12 plays a vital role in the metabolism of fatty acids essential
for the maintenance of myelin.
172
Adenosylcobalamin (B12) is a coenzyme in the reaction involved in
methionine metabolism using methionine synthase reductase (MSR) –
that is further reactions after methionine has been formed. In the MS Metalloporphyrins and
Metalloenzymes
reaction below – CH3-cobalamin is the cofactor.
CH3
SH
S NOTES
CH2 Methionine synthase CH2
N6-Methyl-H4 folate + + H4 folate
CH2 Vitamin B12 Coenzyme
CH2
H C NH3+
H C NH3+
COO-
COO-
Homocysteine
Methionine
H4folate is converted to N5-methyl-H4folate in a number of different

reactions as it acceptsmethyl groups. The methyl group can only be removed
and the H4folate regenerated by the above reaction.
Carboxypeptidases are mammalian digestive Zinc enzymes, with
a molecular weight of 34,600. It catalyses the hydrolysis of the terminal
peptide bond at the carboxyl end of proteins and other peptide chains. It
is also effective toward correspondingly placed ester linkages. It is a
compact globular protein and is a metalloenzyme, having a tightly bound
zinc ion that is essential for its activity. There is a marked preference for
peptide bonds in which the side chain of the terminal residue is aromatic
or a branched aliphatic chain. Carboxypeptidase A have been found in
the pancrease of many mammals including man, but studies were carried
out in the bovine enzyme. The three-dimensional structure of
carboxypeptidase A was elucidated by William Lipscomb at Harvard in
1967. It has a single polypeptide chain of 307 amino acid residues
R O O
H R
N H3N+
N O- + H2O O- O-
H N +
O R H
O R
12.7.1 Structure
The active site of the enzyme contain Zn(II) ion as the central atom. The
Zn(II) center is in distorted square pyramidal geometry. The central atom
is surrounded by two nitrogen atoms from two histidine imidazole
residues, two oxygen atoms from a glutamic acid moiety, and one water
molecule situated at the axial position. The enzyme has a preference
towards the substrates possessing large hydrophobic C-terminal side
chain, e.g., phenylalanine. Here, hydrophobic pocket creating phenyl ring
situated close to the active site. The Presence of alginine, and tyrosine
residue close to the active site, facile substrate binding.
173
H H
O
Metalloenzymes
O
N N Zn C(Glu)
N O
NOTES HN
The carbonyl oxygen atom of the peptide or ester link that is to undergo
hydrolysis becomes coordinated to the Zn atom. This polarizes it in the -
O-C+ sense, thus making the carbon atom more prone to nucleophilic
attack.
The argenine – 145 residue forms a strong hydrogen – bonded linkage to
the terminal carboxyl group.
This accounts for the specificity of the enzyme for catalyzing hydrolysis
of the terminal residue at the carboxyl end of the peptide. It is also results
in a good fit of a large nonpolar side chain on the terminal residue into an
available hydrophobic pocket.
At this point, so – called Michaelis – complex has been formed.
Controversy on bond scission and generation of products, exists. This
concept accounts for the fact that Michaelis complex (a metastable
complex / intermediate) is formed, and only then is the product complex
formed, from which the products promptly dissociate, leaving the
enzyme ready for the next cycle.
This second complex must be one of the species in which there is
an intermediate anhydride involving the carboxyl group of Glu – 270.
Another key mechanism is the generation of Zn-OH group, which
is responsible directly for the attack on the carbonyl carbon atom. The Zn
ion thus serves twice as a lewis acid: once in binding and polarizing the
carboxyl group and again in enhancing the acidity of the bound water
molecule so that it can become the necessary OH nucleophile. There is
indirect evidence for the occurrence of this Zn–OH attack on the mixed
anhydride intermediate from study of model systems.
O
-
Glu O- OOC
HN
H H NH
O
O
Zn O
(His)N N(His)
Arg
O(Gua) Arg O
Ser O -
OOC
Glu O-
NH +NH3
Tyt
O-
NH
Zn O
(His)N N(His)
O
O
O O(Gua) Arg
Ser
Self-Instructional Material Glu O- H
-
OOC Arg
NH
Tyt
HN
H NH
O
O 174
Ser O Zn O
(His)N N(His)
NH Arg
Tyt O(Gua) Arg
Catechol oxidase is a copper oxidase that contains a type III di-copper
cofactor and catalyzes the oxidation of ortho-diphenols into ortho- Metalloporphyrins and
Metalloenzymes
quinones coupled with the reduction of molecular oxygen to water.
OH O
Catechol Oxidase
2 + O2 2 + 2H2O NOTES
OH O
It is present in a variety of species of plants and fungi including sweet

potato and tea leaf. Metalloenzymes with type 3 copper centers are
characterized by their ability to reversibly bind dioxygen at ambient
conditions.
In plants, catechol oxidase plays a key role in enzymatic browning by
catalyzing the oxidation of catechol to o-quinone in the presence of
oxygen, which can rapidly polymerize to form the melanin that grants
damaged fruits their dark brown coloration.
12.8.1 Structure
 It is a globular, single domain monomeric enzyme.
 The active site of catechol oxidase is di-copper center,
 A phenylalanine side-chain (Phe261) is above one of the copper
centers and prevents the substrate from coordinating with both
copper ions in the active site.
 The nitrogens on the imidazole side chains of His88, His109, and
His118 coordinate with the first catalytic copper while the
nitrogens on the imidazole side chains on His240, His244 and
His274 coordinate with the second catalytic copper ion.
 In the oxidized Cu(II)-Cu(II) state, each copper ion possesses a
four coordinate trigonal pyramidal geometry, with the three
histidine residues and a bridging hydroxide molecule forming the
four ligands on each copper ion.
 In the oxidized Cu(II)-Cu(II) state, the Cu-Cu distance is 3.3 Å
while in the reduced Cu(I)-Cu(I) state, the distance increases to
4.4 Å.
 The catalytic cycle begins with the catechol oxidase in its native
oxidized Cu(II)-Cu(II) state with a coordinated hydroxide ion
bridging the two copper centers.
 As catechol enters the active site, a proton is abstracted from one
of the alcohols.
 The catechol coordinates with a Cu(II) center in a monodentate
fashion, displacing one of the coordinating histidine residues.
 The coordinated hydroxide ion abstracts another proton from
catechol to form water, and the catechol is oxidized to o-quinone.
175
The two resulting electrons reduce both copper centers to their
Cu(I)-Cu(I) state.
Metalloenzymes  Dioxygen then binds one copper center, displacing the
coordinated water molecule, and another molecule of catechol
binds to the other copper center, displacing another histidine
residue.
NOTES  This forms a complex in which one copper center has a tetragonal
planar coordination with His240, His244 and the dioxygen
molecule. The other copper center retains its initial tetragonal
pyramidal geometry with dioxygen, His88 and His118 in the
equatorial positions, and His109 in an axial position.
 In this state, the enzyme active site is in a ternary catechol
oxidase–O22−–catechol complex. Two electrons are transferred
from the substrate to the dioxygen, followed by cleavage of the
O–O bond.
 Water is released, and the second o-quinone product is formed
together with the restoration of the initial Cu(II)-Cu(II) state to
complete the catalytic cycle.
+H2O
O His HO
O His
His
CuII CuII HO
His
O His
His
2H+
H+
Oxidized Cu(II)-Cu(II) state
HO HO
O His
O His
His
His O- II CuII
Cu
CuII CuII
His
O His
His
O His His
His
H2O + H+
H2O His His
His
Cu I CuI
O
O
OH His
His
+O2 His
OH
Reduced Cu(I)-Cu(I) state
Check Your Progress

1. What is carbonic anhydrase?
2. What are vitamin B12 and vitamin B12 coenzyme?
3. What is the function of catechol oxidase in plant tissues?
176
 An enzyme present in red blood cells, carbonic anhydrase, aids in
the conversion of carbon dioxide to carbonic acid and bicarbonate Metalloporphyrins and
Metalloenzymes
ions. When red blood cells reach the lungs, the same enzyme
helps to convert the bicarbonate ions back to carbon dioxide,
which we breathe out.
 vitamin B12 (cobalamin) is the coenzyme that affects the cellular NOTES
metabolism and works together with the vitamin B9 folate to
synthesize nucleic acids, helps to maintain healthy blood cells,
maintains the nervous system, and helps prevent types of anemia.
 In plants, catechol oxidase plays a key role in enzymatic
browning by catalyzing the oxidation of catechol to o-quinone in
the presence of oxygen, which can rapidly polymerize to form the
melanin that grants damaged fruits their dark brown coloration.
12.10 Summary
 Metalloenzymes - contain definite quantity of functional metal
ion that is retained throughout purification.
 Chlorophyll is the molecule that absorbs sunlight and uses its
energy to synthesise carbohydrates from CO2 and water.
 Haemoglobin is an effective buffer for blood. The buffering
capacity is due to the presence of ionisable groups in the
imidazole side chain of histidine residues. Cellular oxygen is
stored by Myoglobin, until it is required for metabolic action.
 Cytochromes are membrane-bound (i.e., inner mitochondrial
membrane) heme proteins containing heme groups and are
primarily responsible for the generation of ATP via electron
transport and catalysis by reduction or oxidation of their heme
iron. Enzymes are biologically active proteins that accelerate the
breakdown of food that is eaten. Enzymes are biological catalysts.
 Coenzyme B12 is based on the Co(III)-corrin ring with a 5‘-
deoxyadenosyl group bound to the Co(III).
 Coenzymes bind to an apo-enzyme to form a holoenzyme that is
biologically active. The Co changes between Co(I), Co(II), and
Co(III) in its reactions.
 Carboxypeptidases are mammalian digestive Zinc enzymes,
 Catechol oxidase is a copper oxidase that contains a type III di-
copper cofactor and catalyzes the oxidation of ortho-diphenols
into ortho-quinones coupled with the reduction of molecular
oxygen to water.
12.11 Keywords
 Chlorophyll: Chlorophyll is the molecule that absorbs sunlight
and uses its energy to synthesise carbohydrates from CO2 and
water.
177
 The Bohr effect: The pH-sensitivity as well as the progressive
increase of O2 binding constants in Hb are due to the interaction
Metalloenzymes between the subunits
 Vitamin B12 is the only known essential biomolecule with a
stable metal-carbon bond, that is, it is an organometallic
compound
NOTES  Catechol oxidase is a copper oxidase that catalyzes the oxidation
of ortho-diphenols into ortho-quinones coupled with the reduction
of molecular oxygen to water.
1. What is the function of chlorophyll
2. Write short notes on structure of Haemoglobin
3. Differentiate metaloenzyme and metalloprotein
4. Describe the biological activity of zinc containing enzyme
1. Gerdemann C, Eicken C, Krebs B (March 2002). "The crystal
structure of catechol oxidase: new insight into the function of
type-3 copper proteins". Accounts of Chemical Research. 35 (3):
183–91.
2. G. S.Sodhi. Inorganic Chemistry,.IstEdition, VB (P) Ltd, 2006.
3. John C. Kotz, Paul M. Treichel, John Townsend , Chemistry &
Chemical Reactivity,, 8th ed. Cengage Learning, USA, 2012.
178
UNIT-13 NON-HEME IRON PROTEINS
Structure Non-Heme Iron Proteins
13.0 Introduction
13.1 Objective
13.2.1 Rubredoxins [1Fe-0S] proteins
NOTES
13.2.2 Two-Iron Ferredoxins [2Fe-2S] proteins
13.2.3 3Fe–4S clusters
13.4. Check your progress question
13.6 Keywords
13.7 Summary
13.0 Introduction
Non-heme iron proteins:Rubredoxins, ferredoxins, hemerythrin,
aconitase, and high-potential iron proteins are Non-heme iron proteins,
which contain strongly bound functional iron atoms attached to sulfur,
but they do not contain porphyrins. Heme iron is typically absorbed at a
higher rate than non-heme iron, which means that the body more easily
absorbs iron from animal products than iron derived from plant foods.
Iron–sulfur proteins are proteins characterized by the presence of
iron–sulfur clusters containing sulfide-linked di-, tri-, and tetrairon
centers in variable oxidation states. The iron-sulfur proteins occurs
extensively in all living organisms and take part in a wide range of
electron-transfer processes, either as redox centers (e. g. ferredoxins,
rubredoxins) or as catalysts (e.g. hydrogenase, nitrogenase, etc). Iron–
sulfur clusters are found in a variety of metalloproteins, such as the
ferredoxins, as well as NADH dehydrogenase, hydrogenases, coenzyme
Q – cytochrome c reductase, succinate – coenzyme Q reductase and
nitrogenase. Additionally, some Fe–S proteins regulate gene expression.
Fe–S proteins are vulnerable to attack by biogenic nitric oxide, forming
dinitrosyl iron complexes. In most Fe–S proteins, the terminal ligands on
Fe are thiolate, but exceptions exist.
Iron sulfur proteins are found to be of low molecular weight
(6000-20,000) and contain iron, cysteinyl sulfurs (coming from the
amino acid cysteine in the protein chain) and 'inorganic
sulfur', the so called non-cysteinyl sulfur atoms. The sulfur ligands are
arranged tetrahedrally about the iron atoms. The presence of inorganic
sulfur is indicated through the release of H2S gas when these proteins are
treated with a mineral acid. The cluster of iron and inorganic sulfur atoms
in the form FenSn, or (nFe-n'S) where n and n' are 1,0; 2,2; 3,4; 4,4
179
respectively constitutes the core group in these proteins and are their
redox centres. These redox centres are wrapped in the protein chain with
Non-Heme Iron Proteins
the cysteinyl sulfurs of the protein coordinating to theirons of the core
group. These proteins may be categorised into five accepted classes of
Fe-S centres, according to the numbers of iron and inorganic sulfur atoms
in the cluster.
NOTES 13.1 Objective
After going through the unit you will be able to
o Understand the structural motifs of iron-sulfur proteins
o Relate the mechanism of iron-sulfur proteins
o Value the role and importance of nitrogenase enzyme
In almost all Fe–S proteins, the Fe centers are tetrahedral and the
terminal ligands are thiolato sulfur centers from cysteinyl residues. The
sulfide groups are either two- or three-coordinated.
13.2.1 Rubredoxins [1Fe-0S] proteins
Iron-sulfur proteins with no bridging sulfur (0S) or sulfide atom is
known as rubredoxins. It is mainly found in bacteria and acts as one
electron donor-acceptor. The arrangement around the iron center is
tetrahedral and the Fe(II) center is surrounded by four sulfur atoms from
four cystine (Cys) residues present in the protein chain of 55 amino acids.
The redox centre is made up of only high spin Fe(III) and there are no
inorganic sulfur atoms in the core group.The Fe-S distances range from
2.24 to 2.33 AO and the S-Fe-S angles from 104 to 114O. When the Fe
(III) is reduced to Fe (II) there is a slight (0.05Ao) increase in the Fe-S
distances but the essentially tetrahedron coordination is maintained.
Mossbauer spectroscopy has shown that the iron is in the high spin
condition in both oxidation complexes, to understand the properties of
rubredoxins.
S(Cys)
(Cys)S Fe(II) S(Cys)
S(Cys)
13.2.2 Two-Iron Ferredoxins [2Fe-2S] proteins

Ferredoxins are most important family of iron-sulfur proteins.
Three major categories of ferredoxins are, [2Fe-2S], [3Fe-4S], and [4Fe-
4S]. The [4Fe-4S] is most important. Ferredoxins and high potential iron
proteins are also relatively small proteins of molecular weight 6000 –
12,000. Isolated from mammals, plants, and bacteria. Both the iron
centers are in tetrahedral coordination environment and linked by two
inorganic sulfide bridges. Both Fe(III) centers are antiferromagnetically
coupled to each other. Hence, a diamagnetic ground state results. After
accepting a electron one center becomes Fe(II) and the other is Fe(III).
180
After antiferromagnetic coupling between the S = ½ ground state
appeared. The oxidized proteins contain two Fe3+ ions, whereas the
reduced proteins contain one Fe3+ and one Fe2+ ion. These species exist Non-Heme Iron Proteins
in two oxidation states, (FeIII)2 and FeIIIFeII. Spectroscopic evidence

shows that in [2Fe-2S]+ cluster, the added electron is localized on one
iron atom, so that one FeII and one FeIII are present. In the [2Fe-2S]2+
cluster, the Fe to Fe distance is only 2.72Ao and the two high spin (d5) Fe NOTES
atoms have their magnetic moments so strongly coupled antiferro
magnetically that the cluster is diamagnetic.
(Cys)S S S(Cys)
[2Fe-2S]2+ + e- [2Fe-2S]1+
Fe(III) Fe(III) 2Fe(III)
E = 0 to -0.4 V Fe(II) Fe(III)
(Cys)S S S(Cys)

Proteins are also known to contain [Fe3S4] centres, which feature
one iron less than the more common [Fe4S4] cores. The structure is a
distorted cubic core. T hree sulfide ions bridge two iron ions each, while the
fourth sulfide bridges three iron ions. All the iron centers are tetrahedral.
Their formal oxidation states may vary from [Fe3S4]+ (all-Fe3+ form) to
[Fe3S4]2− (all-Fe2+ form). In a number of iron–sulfur proteins, the [Fe4S4]
cluster can be reversibly converted by oxidation and loss of one iron ion
to a [Fe3S4] cluster. E.g., the inactive form of aconitase possesses an
[Fe3S4] and is activated by addition of Fe2+ and reductant. It is found is
several iron containing metalloenzymes like nitrogenase, hydrogenase, etc.. and
also in pig heart. All the iron centers are in tetrahedral coordination
environment and linked with each other by two inorganic sulfide bridges.
S(Cys)
Fe
S S
S [3Fe-4S]1+ + e- [3Fe-2S]0
3Fe(III) Fe(II) 2Fe(III)
Fe(III) Fe(III) E = +0.1 to -0.4 V
(Cys)S S S(Cys)
1+
[3Fe-4S]

A common motif features a four iron ions and four sulfide ions placed
at the vertices of a cubane-type cluster. The Fe centers are typically further
coordinated by cysteinyl ligands. The [Fe4S4] electron-transfer proteins ([Fe4S4]
ferredoxins) may be further subdivided into low-potential (bacterial-type) and
high-potential (HiPIP) ferredoxins. Low- and high-potential ferredoxins are
181
related by the redox scheme. In HiPIP, the cluster shuttles between [2Fe3+,
2Fe2+] (Fe4S42+) and [3Fe3+, Fe2+] (Fe4S43+). The potentials for this redox couple
range from 0.4 to 0.1 V. In the bacterial ferredoxins, the pair of oxidation states
are [Fe3+, 3Fe2+] (Fe4S4+) and [2Fe3+, 2Fe2+] (Fe4S42+). The potentials for this
redox couple range from −0.3 to −0.7 V. The two families of 4Fe–4S clusters
share the Fe4S42+ oxidation state. The difference in the redox couples is
NOTES
attributed to the degree of hydrogen bonding, which strongly modifies the
basicity of the cysteinyl thiolate ligands. A further redox couple, which is still
more reducing than the bacterial ferredoxins is implicated in the nitrogenase.
S(Cys)
S Fe
(Cys)S Fe S + e-
[4Fe-4S]2+ [4Fe-2S]0
(Cys)S Fe S 2Fe(II)2Fe(III) E = +0.1 to -0.4 V 2Fe(II) 3Fe(III)
S Fe
S(Cys)
[4Fe-4S]2+
A schematic diagram of the redox potential of the various FeS centers in

comparison with other known redox centers.
Nitrogen fixation is a process by which nitrogen in the air is
converted into ammonia (NH3) or related nitrogenous compounds.
Atmospheric nitrogen is molecular dinitrogen, a relatively nonreactive
molecule that is metabolically useless to all but a few microorganisms.
Biological nitrogen fixation converts N2 into ammonia, which is
182
metabolized by most organisms. Nitrogen fixation is essential to life
because fixed inorganic nitrogen compounds are required for the
biosynthesis of all nitrogen-containing organic compounds, such as Non-Heme Iron Proteins
amino acids and proteins, nucleoside triphosphates and nucleic acids. As
part of the nitrogen cycle, it is essential for agriculture and the
manufacture of fertilizer. It is also, indirectly, relevant to the manufacture
of all chemical compounds that contain nitrogen, which includes
NOTES
explosives, most pharmaceuticals, and dyes.
Nitrogen fixation is carried out naturally in the soil by a wide range of
microorganisms termed diazotrophs that include bacteria such as
Azotobacter, and archaea. Some nitrogen-fixing bacteria have symbiotic
relationships with some plant groups, especially legumes. Looser non-
symbiotic relationships between diazotrophs and plants are often referred
to as associative, as seen in nitrogen fixation on rice roots. Nitrogen
fixation also occurs between some termites and fungi. It also occurs
naturally in the air by means of NOx production by lightning.
All biological nitrogen fixation is effected by enzymes called
nitrogenases. These enzymes contain iron, often with a second metal,
usually molybdenum but sometimes vanadium. Molecular nitrogen (N2)
is so unresponsive to ordinary chemical reactions that it has been
characterized as ‗almost as inert as a noble gas‘. The very large triple
bond energy (945KJ/mol) tends to make the activation energy
prohibitively large.The common Haber process requires about 20 MPa
pressure and 500°C temperature to proceed, even in the presence of the
best Haber catalyst. But the fixation of atmospheric dinitrogen occurs
readily in various bacteria, blue green algae, yeasts and in symbiotic
bacteria – legume associations under mild conditions.
There are several bacteria and blue – green algae that can fix
molecular nitrogen in vivo. Both free living species and symbiotic
species are involved the strictly anaerobic Clostridium pasteurianum,
aerobes like Klebsiella pneumoniae and strict aerobes like Azotobacter
vinlandii. Even in the aerobic forms it appears that the nitrogen fixation
takes place under essentially anaerobic conditions.
The most important nitrogen – fixing species are the mutualistic
species of Rhizobium living in root nodules of various species of
legumes (clover, alfalfa, beans, peas, etc).
The active enzyme in nitrogen fixation is nitrogenase. Two
proteins are involved. The smaller has a molecular weight of 57,000 –
73,000. It contains an Fe4S4 cluster. The larger protein is an 22
tetramer with a molecular weight of 220,000 – 240,000 containing two
molybdenum atoms, about 30 iron atoms and about 30 labile sulfide ions.
The iron – sulfur clusters probably act as redox centers. It is possible to
isolate a soluble protein – free cofactor containing molybdenum and iron.
183
Recombination of the cofactor with inactive nitrogenase restores the
activity.
It seems likely that the active site for dinitrogen binding involves
the molybdenum atom. It has been established by EXAFS that the
coordination sphere consists of several sulphur atoms at distances of
about 235pm. An Mo=O double bond, so common in complexes of
NOTES Mo(IV) and Mo(VI), is not present. There are other heavy atoms,
perhaps iron, nearby (~270pm).
The ultimate source of reductive capacity is pyruvate, and the
electrons are transferred via ferredoxin to nitrogenase. There is some
evidence, not strong, that Mo(III) is involved. Two Mo(III) atoms
cycling through Mo(VI) would provide the six electrons necessary for
reduction of dinitrogen.
Alternatively, since the enzyme is rich in ferredoxin – type
clusters, there should be a ready flow of electrons, and the molybdenum
may stay in the one or two oxidation states that most readily bind
dinitrogen and its intermediate reductants. The overall catalytic cycle
may be represented as,

1. Compare the different types of iron sulfur protein
2. What is meant my nitrogen fixation?
1. Iron–sulfur proteins are proteins characterized by the presence of iron–
sulfur clusters containing sulfide-linked di-, tri-, and tetrairon centers in
variable oxidation states. The iron-sulfur proteins occurs extensively in
all living organisms and take part in a wide range of electron-transfer
processes, either as redox centers (e. g. ferredoxins, rubredoxins) or as
catalysts (e.g. hydrogenase, nitrogenase, etc).
184
2. Nitrogen fixation is a process by which nitrogen in the air is
converted into ammonia (NH3) or related nitrogenous compounds.
13.6 Keywords Non-Heme Iron Proteins
Rubredoxins [1Fe-0S] proteins: Iron-sulfur proteins with no bridging
sulfur (0S) or sulfide atom is known as rubredoxins.
Ferredoxins are most important family of iron-sulfur proteins. Three
major categories of ferredoxins are, [2Fe-2S], [3Fe-4S], and [4Fe-4S]. NOTES
Nitrogen fixation is a process by which nitrogen in the air is converted
into ammonia (NH3) or related nitrogenous compounds.
13.7 Summary
In this unit we discuss about iron-sulfur cluster and nitrogen fixation. The
fact that iron-sulfur clusters occur as an integral component of electron
transfer proteins is an exciting area of bioinorganic chemistry. Now,
more than about thirty years after their initial discovery, Fe-S proteins are
being understood to a certain extent and with more refined techniques
and many more years of work, the exact nature of the ways in which they
operate may be understood. This will result in many openings in
biochemistry, not least of which are the exact nature of nitrogen fixation
and chloroplast function and the implicationswhich will follow if these
are initiated in the laboratory.
1. Explain Non-heme iron proteins
2. Draw the structure of Rubredoxins
3. Describe the function of High potential iron protein
4. What is the advantages of nitrogen fixation.
• R H Holm, S Ciurli and J A Weigel. Progress in Inorganic
Chemistry.38.1, 1990.
• P J Stephens, DR Jollie and A Warshel, Chemical Review, 96. 2491,
1996.
185
UNIT-14: METAL IONS IN BIOLOGY
STRUCTURE
14.0 Introduction
14.1 Objective
14.2 Alkali and Alkaline earth metals in biology
NOTES
14.2.4 Biological Importance of Calcium
14.3.1 Steps involved in the Sodium-Potassium Pump
(Na+-K+ pump)
14.5 Chelating agents in medicine
14. 8 Summary
14.9 Keywords
14.0 Introduction
Twenty five elements are known to be essential for living
organisms, and several more may be biochemically significant. After the
major constituents of organic substances (C, O, H), several groups of
elements may be distinguished.
Classification of minerals found in the human body:
- macroelements (minerals), required in amounts greater than > 100
mg/day
C, H, O, N, S, P, Ca, Mg, Na, K, Cl
- microelements (trace elements), required in amounts less than < 100
mg/day
• essential: Co, Cr, Cu, F, Fe, J, Mn, Mo, Se, Zn
• probably essential: Ni, Si, Sn, V
• nonessential: As, B, Cd, Hg, Pb, Sb …
Functions of metal ions in biological systems
Self-Instructional Material - catalytic (metalloenzymes, metal-activated enzymes)
- Structural (hydroxyapatite)
186
- in hormone action (calcium, iodine)
- in antioxidants (copper, zinc, manganese, selenium)
- as drug components (gold, lithium, platinum) Metal ions in biology
The alkali metals sodium, potassium (Group IA in the Periodic
Table) are essential for a number of processes, including ion transport,
electrical signaling, and electrolyte balance. The alkaline earths
calciumand magnesium (Group IIA) play different roles. Mg is critically
NOTES
linked to phosphate biochemistry, as it binds to ATP and kinases,
enzymes which control ATP activity. It is also important in many
enzymes, and plays the central photo-capture role in chlorophyll.
Calcium is important for cell wall structure, the contraction of muscle
(and other) fibers, and the acquisition and transport of phosphate. It is
involved in cell division and other reproductive processes. Ca is a main
component of common biomineralization structures including oxalates
(in the worst case, kidney stones), phosphates (such as bone and teeth)
and calcium carbonate shells.
14.1 Objective
After going through this unit you will be able to
 Understand the biological importance of Alkali and
Alkaline earth metals
 Explain the concept and mechanism of sodium-potassium
pump
 Discuss about metal ion poison
 Describe about chelating agent in medicine
14. 2 Alkali and Alkaline earth metals in biology
Among the ‗metals of life‘ (ie, biometals), four metals form an
‗island‘ in the periodic table. These are Sodium, Magnesium, Potassium
and Calcium. These four biometals are also called the ‗main group
metals‘. These inorganic elements, especially at trace quantities play a
vital role at the molecular level in a living system. The metals of the main
group are specially involved in maintaining the osmotic balance and
producing skeleton. Some of them may participate in enzymatic
processes.
Sodium and calcium are the main cations outside the cells while
potassium and magnesium are the main ones within the cells and there is
an ion-pump mechanism for driving the ions in the required direction for
maintaining some biological functions such as nerve-impulse
transmission, muscle contraction etc.,
Alkali metal salts are generally soluble but sometimes their
insoluble salts may create some problems, like – insoluble sodium salt of
uric acid causes gout. Similarly, the insoluble salts of calcium as
carbonate, fluoride, oxalate and phosphate sometimes produces troubles
such as clogging of blood streams.
It is one of the most abundant cations in the extracellular part of
mammalian tissues. It is important in nerve impulse transmission and
187
maintenance of osmotic pressure. It is also an essential cation for electro
neutrality. It is moderately toxic when injected intravenously. Sodium
regulates blood volume, blood pressure, neuron function, osmotic
equilibrium & PH. Higher levels of sodium can prevent kidney failure,
loss of fluids, hypothyroidism, heart failure, liver cirrhosis etc. Sodium
plays an important role in the body because it deals with maintaining
NOTES water balance, transmitting nerve impulses and regulating muscle
contraction & relaxation Lodized salt is essential for the body as it helps
in the production of thyroid harmones which affects growth & metabolic
rates
It is required in photosynthesis. In chlorophyll, Mg is present in
the cavity of a porphyrin. Such metallation makes chlorophyll
phosphorescent, but the free porphyrin gives fluorescence emission. This
phosphorescent behaviour is biologically very important, without which
the light energy absorbed will be lost and will not be available for
chemical transformation. For phosphorescence to occur, there must be a
suitable excited state of finite life time so that it has sufficient energy to
transfer the energy for chemical reaction. Probably, through the spin-
orbit coupling phenomenon, mixing of the excited singlet and triplet state
is the source of phosphorescence and of the energy required for
photosynthetic chemical reaction.
 Activity of enzymes: Mg plays a crucial role in the biochemical
reactions occurring in our body. The main role of this ion in the body is
to regulate the functions of enzymes which in turn are responsible for
various chemical reactions. Magnesium as an enzyme co-factor plays an
important role in the breakage of glucose and fat molecules, in the
production of enzymes, proteins and regulation of cholesterol.
 Acts as fuel source: It plays an important role in the production of
energy within the cells. Without the sufficient supply of this ion nutrients
cannot be converted into usable energy or ATP (adenosine triphosphate)
which is the fundamental unit of energy in human body. Production of
ATP is significant to perform various actions such as cell reproduction,
protein synthesis etc.
 Protector of human DNA: DNA synthesis is not possible without
the sufficient supply of this ion. It is responsible for the stability and
proper functioning of DNA.
 To maintain an electrolyte balance: It is one of the most important
mineral in order to maintain a healthy electrolytic balance in our body.
Deficiency of this ion leads to the improper functioning of sodium-
potassium pump.
It is one of the most abundant cations occurring in the
intracellular fluids in mammalian systems. It is important for electrolytic
Self-Instructional Material and osmotic balance. Its proper concentration gradient across the
membrane is extremely useful in the creation and transmission of nerve
188
impulses and in muscle contraction. It is also important in maintaining
proper rhythm of the heart beat. K+ participates as a cofactor in a number
of internal enzymes. It activates pyruvate kinase which is required for Metal ions in biology
glycolysis. It is also required in high concentration for the biosynthesis
of proteins by ribosomes. In taking higher levels of potassium can reduce
the risk of hyper tension, stroke and potassium deficiency as well as
reduce bone turnover in people. Potassium bromated is used to improve
NOTES
dough strength and rise height. Potassium helps move nutrients into cells
and waste products out of cells. Potassium is needed for muscle growth,
nervous system and brain function. Measuring the amount of potassium
by blood test can identify the presence of kidney disease, diabetes, and
vomiting problem in the body. Consumption of foods rich in potassium
plays a role to prevent osteoporosis.
14. 2. 4 Biological Importance of calcium
Like Magnesium, it is also important in controlling different
electrochemical processes such as nerve impulse conduction. Calcium is
mainly found in the bones and teeth of the living beings. It is used in the
construction of cell walls, bones, teeth etc. Ca2+ can antagonize the
potentiating effect of Mg2+ in enzymic processes and hence very
important in the enzyme control mechanism. Blood is a large tank of this
mineral. It participates in the formation of casein from milk and
formation of fibrin from fibrinogen during blood clotting. Deficiency of
calcium increases the blood clotting time. It is also important for the
correct rhythm of heart beat and in lactation. Calcium supports muscle
contraction.The deficiency of this metal leads to disorder of nerves.It
plays a significant role in the metabolism of nitrogen in plants. Absence
of this mineral in the plants affects the size and number of chloroplasts.
A molecular mechanism by which sodium ions are transferred
across a cell membrane by active transport especially one that is
controlled by a specialized plasma membrane protein by which a high
concentration of potassium ions and a low concentration of sodium ions
are maintained within a cell.The process of moving sodium and
potassium ions across the cell membrance is an active transport process
involving the hydrolysis of ATP to provide the necessary energy. It
involves an enzyme referred to as Na+/K+-ATPase. The sodium-
potassium pump is an antiporter transport protein. This pump is
responsible for the usage of almost 30 % of the body's ATP, this is due to
1 molecule of ATP being hydrolysed as three molecules of Na+ are
pumped out of the cell and two molecules of K+ are pumped into the cell.
The sodium-potassium pump is a very important protein in our cell
membranes. The pump can be used to generate ATP when supplies are
low by working in the opposite way. The pump is also used to control the
osmolarity of the cell, by pumping the Na+ out that have diffused into the
cell down their high electrochemical gradient the cell can be kept at
189
osmotic equilibrium. The pump plays a large role in nerve cells and
initiating action potentials. The main function of the N+/K+ ATPase
pump is to maintain resting potential so that the cells will be keeping in a
state of a low concentration of sodium ions and high levels of potassium
ions within the cell. Action potentialscould not occur without these cells.
They initiate the first part of the depolarisation before the voltage-gated
NOTES channels come into play. The sodium-potassium pumps also recover the
axon to its resting state of -60mV after an action potential has passed.
14.3.1 Steps involved in the Sodium-Potassium Pump (Na+-K+
pump)
 3 Na+ ions from inside the cell bind to the Na+-K+ pump
 The pump changes shape, transporting the 3 Na+ ions across the
cell membrane and releases them on the outside of the cell
membrane.
 The pump is now exposed to the outside surface of the cell. 2 K+
ions from outside the cell bind to the pump and the pump changes
shape again.
 K+ ions are transported across the cell membrane and are released
inside the cell
 During this process, ATP is split into ADP and inorganic
phosphate. The breaking of this bond releases energy to power the
pump.
 Overall, because 3 positively charged ions left the cell and only 2
positively charged ions entered the cell, a charge gradient
develops across the cell membrane such that the outside of the
cell has more positive charge and the inside of the cell has more
negative charge.
 A molecule of adenosine triphosphate (ATP, a source of chemical

energy) binds to a site on the intracellular side of the Na +-K+
pump protein.
 Three sodium ions (3 Na+, shown as red balls) from the
cytoplasm bind to ―lock and key‖ sites on the Na+-K+ pump.
 The bound ATP is then split into ADP and inorganic phosphate
(the ADP is released back into the cytoplasm, while the inorganic
phosphate, P, remains bound to the pump). The breaking of this
bond releases energy that powers a change in the shape of the
190
Na+-K+ pump protein , releasing the three sodium ions (3 Na+)
outside the cell.
 Two potassium ions (2 K+) from outside the cell bind to ―lock and Metal ions in biology
key sites‖ on the protein of the Na+-K+ pump.
 The protein of the Na+-K+ pump changes shape again as the
remaining inorganic phosphate group leaves the protein's active
site.
 The two potassium ions (2 K+) are released into the cytoplasm, as NOTES
another ATP molecule binds to the active site on the Na +-K+

pump protein and the process starts over.
 When this process repeats many times, an imbalance of charge
forms across the membrane. There will be more positive charged
ions outside the membrane than inside. This creates a chemical
potential energy which can be used by the cell to later generate
lots more ATP, for generating electrical impulses, or for muscle
contractions.
 Neurons communicate with one another when this charge
difference is used to generate an ―action potential‖ along the
axon of a neuron.
A toxic heavy metal is any relatively dense metal or metalloid that is
noted for its potential toxicity, especially in environmental contexts.
Heavy metals are found naturally in the earth, and become concentrated
as a result of human activities, or, in some cases geochemical processes,
such as accumulation in peat soils that are then released when drained for
agriculture. Common sources are mining and industrial wastes; vehicle
emissions; lead-acid batteries; fertilisers; paints; treated woods; aging
water supply infrastructure, and microplastics floating in the world's
oceans. Heavy metals "can bind to vital cellular components, such as
structural proteins, enzymes, and nucleic acids, and interfere with their
functioning". Symptoms and effects can vary according to the metal or
metal compound, and the dose involved. Broadly, long-term exposure to
toxic heavy metals can have carcinogenic, central and peripheral nervous
system and circulatory effects.
For the industrial purposes many mining metals such as Co, Cu,
Zn, Pu, Be, Cd, etc., are being accumulated in our ecosystem during their
winning, smelting and roasting processes.Mercury is extensively used as
a catalyst in different industries. It is often used as an electrode in the
manufacture of caustic soda, chlorine and in many other electrochemical
processes.It has been proposed that the mercury discharged from
different sources in to the sea undergoes methylation to from methyl
mercury cation (CH3Hg+). The toxicity of CH3Hg+ is much more severe
due to the facts,
i) The organic moiety gives it a lipophilic character so that it can easily
pass through the biological lipid membrance.
191
ii) The Mercury is tightly bound to carbon so that the molecule is not
easily degraded and it may maintain its toxicity for a long time.
Different metallic compounds are used in human diseases and
from such treatments, different toxic metals may be accumulated in our
body
NOTES For examples gold from gold therapy for arthritis, Platinum from
platinum complexes used against cancer, iron from iron containing pills,
arsenic and antimony from the use of organic arsenicals and antimony
based organic compounds for bacterial infections.
Lead alkyls are used extensively to increase the octane
number of gasoline in automobile engines. Ethylene dihalides are used
to promote the formation of lead halides rather than the non – volatile
compounds that would foul the engine.
(C2H5)4Pb + C2H4 X2 + 16 O2 PbX2 + 10 CO2 + 12 H2O
This becomes a potential source of lead poisoing and it is a world
wide problem.
Industrial food processing is becoming a potential source of metal
poisoning.For an example – abrasions on equipments can lead the
processed foods to be contaminated with As, Pb, Cu, Zn, Ni, Hg and Sb.
Use of Nickel as catalyst in the hydrogenation of oils is also worth
mentioning.There are the main sources of metal poisoning.
14.5 Chelating agents in medicine.
Chelating agents are chemical compounds that react with metal

ions to form a stable, water-soluble complex. They are also known as
chelants, chelators, or sequestering agents. Chelating agents have a ring-
like center which forms at least two bonds with the metal ion allowing it
to be excreted.Chelation therapy is the preferred medical treatment for
metal poisoning, including acute mercury, iron, arsenic, lead, uranium,
plutonium and other forms of toxic metal poisoning. The chelating agent
may be administered intravenously, intramuscularly, or orally, depending
on the agent and the type of poisoning.
There are two types of chelation therapy based on the number of
different types of ligands administered.
1. Single Ligand Therapy, 2. Double Ligand Therapy
1. Single Ligand Therapy
To remove a particular toxic metal one selective chelating drug is
administered in this method.
2. Double Ligand Therapy
In this method, two different ligands are simultancously
administered for a particular toxic metal. Based on their mechanism of
Self-Instructional Material action in vivo, it be classified into -.
a. Synergistic chelation Therapy, b. Mixed Ligand Chelation Therapy.
192
Synergistic Chelation Therapy (P.M. May and D.R. Williams,
1979) occurs when one drug mobilies the metal, while the other traps it Metal ions in biology
in plasma to be excreted in the urine.
For an example, ‗puchel‘ and ‗dtpa‘ act synergistically (D.R.
Williams at al, 1984) in a chronic plutonium intoxication. Puchel being
more lipophilic, can mobilize the radionucleides from the sites of Pu – NOTES
deposition and transfer it into the plasma where dtpa can trap the
plutonium to excrete in the urine. It is worth mentioning that the
thermodynamic affinity of dtpa towards plutonium is greater than that of
puchel. Such beneficial combinations of chelating drugs acting
synergistically have been reported.
In this process, two different ligands are introduced in 1:1 molar
ratio, the ligands from ternary complexes with the toxic metal (J.
Schubert and S.K. Deer, 1979). Due to the formation of ternary
complexes, the thermodynamic stabilities are enormously increased due
to many factors such as statistical factors, charge neutralization,
intramolecular electrostatic interactions, cooperative electronic effects,
particularly with the aromatic secondary ligands etc.,
Moreover, due to the formation of a ternary complex, the
pharmacokinetic properties are also significantly changed depending on
the total dentateness of the chelants and the ligancy of the metal. When
the total dentateness is less or greater than the ligancy of the metal ion,
the metal chelates are hydrophilic and they are lipophilic when the total
dentateness is equal to the ligancy of the metal ion. thus, Pu (edta), Pu
(SA), Pu (dtpa) (SA) are hydrophilic and Pu (dtpa), Pu (edta) (SA) are
lipophilic. (SA = Salicylate).
Chelating agents can be used therapeutically to treat problems
caused by the presence of toxic elements. An essential element can be
toxic if present in too great a quantity.
i)Removal of excess of Copper
Wilson‘s disease is a genetic disease involving the buildup of
excessive quantities of copper in the body.Many chelating agents have
been used to remove the excess copper, but one of the best is D –
Penicillamine, HSC (CH3)2 COOH. This chelating agent forms a
complex with copper ions that is coloured an intense purple and
surprisingly has a molecular weight of 2600.
Another surprising fact is that the complex will not from unless
chloride or bromide ions are present and the isolated complex always
contains a small amount of halide.
These puzzling facts were explained by X – ray crystallographic
studies. The structure consists of a central halide ion surrounded by eight
Cu(I) atoms bridged by sulfur ligands. These are in turn coordinated to
193
six Cu(II) atoms. Finally, the chelating amino groups of the
penicillamine complete the coordination sphere of the copper (II) atoms.
ii) An excessive intake of iron causes various problems known as
siderosis. Chelating agents are used to treat the excessive buildup of
iron. In many cases the chelates resemble or are identical to the
analogous compounds used by bacteria to chelate iron. Thus
NOTES desferroxamine B is the drug of choice for African siderosis. The ideal
chelating agent will be specific for the metal to be detoxified. Since a
more general chelating agent is apt to cause problems by altering the
balance of other essential metals. The concepts of hard and soft metal
ions and ligands can be used to aid in this process of designing
therapeutic chelators.
iii) A slightly different mode of therepy involves the use of cis –
diamminedichloro platinum (II), Pt(NH3)2Cl2 and related bis (amine)
complexes in the treatment of cancer.
The exact action of the drug is not known, but only the cis-isomer
is active at low concentrations, not the trans isomer. It is thought that the
platinum binds to DNA, with the chloride ions first being replaced by
water molecules and then by DNA base such as guanine.Studies in vitro
with nucleotide bases as well as theoretical calculations indicate that the
N7 position of guanine is the favoured site for platinum coordination.
The cis-diamine mocity can bind to groups about 280 pm apart. The
most important interaction is interstrand linking of two adjacent guanine
bases on the DNA chain by the plutonium atom. The binding of cisplatin
to DNA would seriously interfere with the ability of the guanine bases to
undergo Waston – Crick base pairing. Thus, when a self complementary
oligomer (a portion of the DNA Chain) reacts with the cis – isomer, two
adjacent guanines are bound and Watson – Crick base pairing is
disrupted.
For cis – diammine dichloroplatinum (II) to work according to the

proposed mechanism, it must hydrolyse in the chromosomes and not in
blood. Fortunately, the blood is approximately 0.1 M in chloride ion,
inhibiting its hydrolysis in blood. In the cytoplasam, the chloride ion
194
concentration is only 4 mM. Thus, hydrolysis and subsequent reactions
with the appropriate biological targets can readily take place.
14.6 Check your progress questions Metal ions in biology
1. Write the functions of metal ions in biological systems
2. Give Biological importance of Sodium
3. Describe Metal Ion Poisoning
4. Explain the mechanism of Sodium ion pump NOTES
1. catalytic (metalloenzymes, metal-activated enzymes)
Structural (hydroxyapatite)
in hormone action (calcium, iodine)
in antioxidants (copper, zinc, manganese, selenium)
as drug components (gold, lithium, platinum).
2. It is one of the most abundant cations in the extracellular part of
mammalian tissues. It is important in nerve impulse transmission and
maintenance of osmotic pressure. It is also an essential cation for electro
neutrality.
3. A toxic heavy metal is any relatively dense metal or metalloid that is
noted for its potential toxicity, especially in environmental contexts.
4. A molecular mechanism by which sodium ions are transferred across a
cell membrane by active transport especially one that is controlled by a
specialized plasma membrane protein by which a high concentration of
potassium ions and a low concentration of sodium ions are maintained
within a cell.The process of moving sodium and potassium ions across
the cell membrance is an active transport process involving the
hydrolysis of ATP to provide the necessary energy.
14.8 SUMMARY
 Among the ‗metals of life‘ (ie, biometals), four metals form an
‗island‘ in the periodic table. These are Sodium, Magnesium,
Potassium and Calcium.
 Higher levels of sodium can prevent kidney failure, loss of fluids,
hypothyroidism, heart failure, liver cirrhosis etc.,
 In chlorophyll, Mg is present in the cavity of a porphyrin. Such
metallation makes chlorophyll phosphorescent and it is one of the
most important mineral in order to maintain a healthy electrolytic
balance in our body.
 Potassium is one of the most abundant cations occurring in the
intracellular fluids in mammalian systems. It is also important in
maintaining proper rhythm of the heart beat. K+ participates as a
cofactor in a number of internal enzymes.
 The process of moving sodium and potassium ions across the cell
membrance is an active transport process involving the hydrolysis
of ATP to provide the necessary energy. It involves an enzyme
referred to as Na+/K+-ATPase.
195
 A toxic heavy metal is any relatively dense metal or metalloid
that is noted for its potential toxicity, especially in environmental
contexts.
 Chelating agents have a ring-like center which forms at least two
bonds with the metal ion allowing it to be excreted.Chelation
therapy is the preferred medical treatment for metal poisoning,
NOTES including acute mercury, iron, arsenic, lead, uranium, plutonium
and other forms of toxic metal poisoning.
 cis – diamminedichloro platinum(II), Pt(NH3)2Cl2 and related bis
(amine) complexes used for the treatment of cancer.
14.9 Keywords
Sodium ion pump: A molecular mechanism by which sodium ions
are transferred across a cell membrane by active transport especially one
that is controlled by a specialized plasma membrane protein by which a
high concentration of potassium ions and a low concentration of sodium
ions are maintained within a cell.
Heavy metal: A toxic heavy metal is any relatively dense metal or
metalloid that is noted for its potential toxicity, especially in
environmental contexts.
Chelating agents: Chelating agents are chemical compounds that react
with metal ions to form a stable, water-soluble complex. They are also
known as chelants, chelators, or sequestering agents.
Cis platin: cis – diamminedichloro platinum (II), Pt(NH3)2Cl2
14.10 Self Assessment Question and Exercise
Short answer question
1. How many Na+ ions are being pumped out?
2. Is more sodium inside the cell?
3. Define heavy metals
4. What is meant by chelation
Long answer question
1. Discuss detail about biological importance of Alkali and
Alkaline earth metals
2. Describe briefly about sodium-potassium ion pumb
3. Explain about chelating agent in medicine
14. 11 Further Reading
1. Frausto da Silva and Willams, The Biological Chemistry of the
Elements, 1991.
2. Alberts B, Johnson A, Lewis J, Raff M, Roberts K, Walter P
Molecular Biology of the Cell. Garland Science, Fifth Edition 2008.
3. Beauge, L. A., Gadsby, D. C., and Garrahan, P. J. Na/K-ATPase and
Related Transport ATPases: Structure, Mechanism and Regulation
(eds.Annals New York Academy Sci., New York, 834, 1997.
4. Jorgensen, P. L. in Molecular Aspects of Transport Proteins (ed. De
Pont, J. J. H. M. M.) Elsevier Service Publisher B.V., 1,1992.
196
ALAGAPPA UNIVERSITY DISTANCE EDUCATION
M.Sc. Degree Examination Third Semester Chemistry Sub. Code: 34431
Advanced Inorganic Chemistry(CBCS 2018 – 19 Academic year onwards)
Time: Three hours Maximum: 75 marks
SECTION A Answer All Questions (10 X2 = 20)
1. Explain chelate effect
2. Describe stability constant of coordination complexes
3. Give one example for hydrolysis in octahedral complexes
4. Explain electron transfer reaction
5. What is meant by two electron transfer reaction
6. Explain term symbol
7. What is spinel?
8. Define cluster?
9. How will you synthesis metal alkyene complexes ?
10. Explain Metallcene
SECTION B Answer ALL questions, choosing either (a) or (b) (5 × 5 = 25)
11. (a) What are inner sphere and outer sphere complexes? Explain them
with suitable mechanisms.
(or)
(b) What are anation reactions? Give the mechanism.
12. (a) What are complementary and non-complementary electro transferreactions?
(or)
(b) What are labile and inert complexes? Give one example each.
13. (a) Give the role of group vibrational frequencies of ligands in the
studyof metal complexes.
(or)
(b) Discuss the bonding in acetylene complexes with suitable examples.
14. (a) Describe the mechanism of hydroformylation reactions?
(or)
(b) Explain the reactivity of ferrocence.
15. (a) Discuss in detail about Non-heme iron proteins
(or)
(b) Discuss briefly the working of sodium ion pump.
SECTION C Answer any THREE questions (3 × 10 = 30)
16. What is stability constant? How is it determined bypH metric and spectrophotometric methods?
17. (a) Describe the mechanism of Ziegler-Natta polymerisation.
(b) Discus briefly on metal-olefin complexes.
18. Discuss briefly the structure and functions of hemoglobin and myoglobin.
19. (a) Construct the orgel diagram for a d9configuration and explain
(b) Give the significance of Racah parameters.
20. Explain the following
a. Wade‘s rule
b. Trans effect
c. Vitamine B12.
197

PG M.sc. Chemistry 34431 Advanced Inorganic Chemistry

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PG M.sc. Chemistry 34431 Advanced Inorganic Chemistry

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ALAGAPPA UNIVERSITY

[Accredited with ’A+’ Grade by NAAC (CGPA:3.64) in the Third Cycle

KARAIKUDI – 630 003

DIRECTORATE OF DISTANCE EDUCATION

ADVANCED INORGANIC CHEMISTRY

Copy Right Reserved For Private use only

“The Copyright shall be vested with Alagappa University”

BLOCK-3 ORGANOMETALLIC CHEMISTRY

Unit -4: Spectral properties of complexes 47 – 63

UNIT-14: Metal ions in biology 186-196

UNIT-1 STABILITY OF COORDINATION COMPOUNDS

[M(H2O)x]n+ + L- [M(H2O)x-1L](n-1)+ + H2O

M +2L  ML2,  2 

Thus M + nL  MLn,  n = n 

The equilibrium constants,  1,  2,  3, .......... are called stepwise formation

From above relation, it is clear that the overall stability constant n is

complexes are as under:

the conclusions, provided the activity of the water is maintained constant.

Basic Ligand Acid

Basic Ligand Metal ion

The first dissociation (1) is expected to be slower than a similar

1.6 Check Your Progress

The characteristics of this reaction are,

intermediate involves the movement of atleast two metal ligand bonds

The second type of intermediate is formed if the nucleophile Y

2.2.1 Labile & Inert Complex

Cu(NH3)4(H2O)22+ + 4H+ + 4Cl- CuCl42- + 4NH4+ + 2H2O

Inert complexes undergoing substitution with t ½> 1 minute. Inert doesn‘t

[Fe(H2O)5F]2+ = labile, but it is very thermodynamically stable

2.2.2 Factors affecting the labile/inert nature of complexes

[Ni(H2O)6]2+ + 6 NH3 [Ni(NH3)6]2+ + 6H2O

Fe(H2O)6]3+ + SCN- [Fe(H2O)5(SCN)]2+ + H2O

[Fe(H2O)6]3+ + Cl- [Fe(H2O)5(Cl)]2+ + H2O NOTES

[Fe(H2O)5(Cl)]2+ + PO43- Fe(H2O)5(PO4) + Cl-

Fe(H2O)5(PO4)+ SCN- [Fe(H2O)5(SCN)]2+ + PO43-

[Fe(H2O)5(SCN)]2+ + F- [Fe(H2O)5(F)]2+ + SCN-

Ligand substitution reactions involving [M(H2O)m]n+ are rapid and

[M(H2O)m]n+ + H218O [M(H2O)m-1(H218O)]n+ + H2O

Generally two observations can be drawn:

2.3.3 Aquation In Octahedral Complexes (AcidHydrolysis)

Factors affecting these reactions

Steric effects of inert (non-leaving) ligands

2.4 Substitution Reactions In Square Planar Complexes.

Square planar complexes with d8 configurations undergo substitution

The trigonal bipyramidal species that forms during the reaction

Reaction coordinate/energy profile for a square planar substitution

2. There exists a parallelism between the reactivity of the square

4. Nature of the entering ligand greatly affects the rate of

NOTES 6. It has been observed that substitution in Pt(II) square planar

7. As the bulkiness of the ligands other than the entering and

[PtA3X]n+withY-to yield [PtA3Y]n+is occurring by a two path mechanism,

The upper path is the solvent path (also called Y-independent

4. Effect of charge on the complex

2.4.1 Trans Effect

Another application of trans effect is in distinguishing cis and

The formation of dπ – pπ bond between Pt(II) and the π- bonding ligand,

3) Molecular Orbital approach

NOTES Cis Effect

2.5 Electron Transfer Reactions Or Redox Reactions