328 A Textbook of Inorganic Chemistry – Volume I

 Charge Transfer Spectra

A charge transfer band may be defined as the peak arising from the transition in which an electron
is transferred from one atom or group in the molecule to another one.
In other words, the transition occurs between molecular orbitals that are essentially centered on
different atoms or groups. These transitions are neither Laporte nor spin-forbidden in nature; and therefore,
show very intense absorption. Charge transfer transitions are primarily classified in four types as:
 Ligand to Metal Charge Transfer
The ligand to metal charge transfer (LMCT) in metal complexes arises when the electrons are
transferred from a molecular orbital with a ligand-like character to those with metal-like character. This type
of transfer is predominant if the following conditions are fulfilled:
i) The ligands should have lone pair of electrons with relatively high-energy such as O2−, Cl−, Br−, S2− or Se.
ii) The metal should be in a high oxidation state and must have low-lying empty orbitals.
These conditions imply that the acceptor level is available and low in energy. Moreover, the charge
transfer transitions for octahedral and tetrahedral complexes are different; therefore, these two types of ligand
to metal charge transfer are quite important and must be discussed in detail.
1. LMCT in octahedral complexes: Before we discuss the ligand to metal charge transfer in octahedral
complexes, the molecular orbital diagram for σ and π-bonding in ML6 geometry should be recalled. The
electrons can be excited, not only from the t2g* to eg* but also from the bonding molecular orbitals of σ and π
nature that are predominantly associated with the ligands. The latter two types of excitation modes result in

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 329

the charge transfer spectra, labeled as the ligand to metal charge transfer. This type of transition results in a
formal reduction of the metal.

Figure 71. Ligand to metal charge transfer in octahedral (ML6) complexes.

Consider a d6 octahedral complex, such as [Co(NH3)5(X)]2+ (X = F−, Cl−, Br− or I−), whose t2g* levels
are filled. As a consequence, an intense absorption band in [Co(NH3)5F]2+ is observed above 40000 cm−1; and
that is corresponding to a transition from ligand σ-bonding molecular orbital to the empty eg* molecular orbital.
However, in [Co(NH3)5Cl]2+ this intense band with two components is observed above 30000 cm−1.
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 330 A Textbook of Inorganic Chemistry – Volume I

Figure 72. The UV-visible absorption spectra of [Co(NH3)5(X)]2+ (X = F−, Cl−, Br− or I−).

The charge-transfer bands appear at lower energy for [Co(NH3)5Br]2+and at still lower energy for
[Co(NH3)5I]2+, overlapping with ligand-field bands and masking their higher energy peaks. It must be noted
that the ligand-field peaks shift slightly according to the increasing strength of the crystal field of X, but the
charge-transfer bands show very large shifts. The shifts in the energies of the LMCT transitions in
[Co(NH3)5(X)]2+ correspond to the changes in ease of removal of the electron (oxidation) from X−. Though the
transition corresponds to the transfer of an electron from X− to Co3+; and therefore, no net oxidation-reduction
occurs because of the very short lifetime of the excited state. Nonetheless, this process, provide a mechanism
for photochemical decomposition that occurs for many complexes stored in strong light. A similar pattern has
been observed in the case of [Cr(NH3)5(X)]2+ (X = F−, Cl−, Br− or I−).
2. LMCT in tetrahedral complexes: Before we discuss the ligand to metal charge transfer in tetrahedral
complexes, the molecular orbital diagram for σ and π-bonding in ML4 geometry should be recalled. The
electrons can be excited, not only from the e* to t2*, but also from the π-bonding molecular orbitals of t2-
symmetry and nonbonding π-SALCs of t1-symmetry; both of which are predominantly associated with the
ligands. The latter two types of excitation modes result in the charge transfer spectra, labeled as the ligand to
metal charge transfer. This type of transition results in a formal reduction of the metal.

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 331

Figure 73. Ligand to metal charge transfer in tetrahedral (ML4) complexes.

Consider a d0 tetrahedral complex, such as MnO4−, whose e* and t2* levels are totally empty. As a
consequence, very intense absorption spectra in permanganate is obtained and all of the four ligand-to-metal-
charge-transfer (LMCT) transitions are observed. However, it must be noted that three out of four peaks happen
to arise in the ultra-violet region and only t1 → e* transition belongs to the visible range. Moreover, this
particular transition is also responsible for the deep purple color of permanganate ion.

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 332 A Textbook of Inorganic Chemistry – Volume I

Figure 74. The UV-visible absorption spectra of MnO4−.

The complete profile of absorption spectra of MnO4− ion is given below as:

Table 15. The type of transition and their wavenumbers of the absorption peaks for MnO4−.

Transition type Wavenumber (cm−1)

L(t1) → M(e*) 17700

L(t1) → M(t2*) 29500

L(t2) → M(e*) 30300

L(t2) → M(t2*) 44400

A similar pattern has been observed in the case of CrO42−. The energies of transitions correlate with the order
of the electrochemical series. Lower energy absorption is expected for the metal ions which are reduced more
easily. The abovementioned trend is in accordance to the transfer of electrons from the ligand to the metal, and
hence resulting in a reduction of the metal center by the ligand attached.

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 333

 Metal to Ligand Charge Transfer

The metal to ligand charge transfer (MLCT) in metal complexes arises when the electrons are
transferred from a molecular orbital with a metal-like character to those with a ligand-like character. This type
of transfer is predominant if the following conditions are fulfilled:
i) The ligands should have high-energy empty π* orbitals such as CO, CN−, SCN− or NO.
ii) The metal should be in a low oxidation state and must have high-lying filled orbitals.
These conditions imply that the empty π* orbitals on the ligands become the acceptor orbitals on the
absorption of light. The available acceptor level is relatively high in energy. However, before we discuss the
ligand to metal charge transfer in transition metal complexes, the molecular orbital diagram for σ and π-
bonding in ML6 geometry should be recalled.

Figure 75. Metal to ligand charge transfer in octahedral (ML6) complexes.

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 334 A Textbook of Inorganic Chemistry – Volume I

The electrons can be excited, not only from the t2g to eg*, but also from the bonding molecular orbitals
of π and antibonding molecular orbitals of σ nature (predominantly associated with the ligands) to antibonding
π*. The latter two types of excitation modes result in the charge transfer spectra, labeled as the metal to ligand
charge transfer. This type of transition results in formal reduction of the metal. The common type of ligands
taking part in MLCT include 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), CO, CN− and SCN−.
Examples of these complexes include: Tris(2,2’-bipyridyl) ruthenium(II), W(CO)4(phen), K4[Fe(CN)6],
K3[Fe(CN)6], [Fe(phen)3]3+, [Fe(acac)3] and Fe(CO)3(bipy).
An orange-colored complex of bivalent ruthenium, [Ru(bpy)3]2+, is being analyzed because the
excited electronic state that results from this charge transfer has an average life-time around microseconds and
the complex can act as an adaptable photochemical reagent. The photo-reactivity of these complexes arises
from the nature of the reduced ligand and oxidized metal center. Now although the states of MLCT complexes
such as [Ru(bipy)3]2+ and Re(bipy)(CO)3Cl were intrinsically not that much reactive, there are many MLCT
complexes which are characterized by reactive MLCT states. Vogler and Kunkely proposed that a MLCT
complex can be considered as an isomer of the ground state, that possesses a reduced ligand and oxidized
metal. Hence, many reactions like electrophilic attack, oxidative addition at the metal ion due to the reduced
ligand, the radical reactions on the reduced ligand, or the outer-sphere charge-transfer reactions can be
attributed to states arising from metal-to-ligand-charge-transfer transitions. The reactivity of MLCT states
usually depends on the oxidation of the metal center. The succeeding processes include exciplex formation,
cleavage of metal-metal bonds, associative ligand substitution.
 Metal to Metal Charge Transfer
The metal to metal or inter-valence charge transfer may simply be defined as the excitation and
subsequent transfer of an electron from a low oxidation state cation to a neighboring cation of a higher
oxidation state.
The transfer is usually excited by a certain visible portion of the light of and produces a characteristic
color. The electron then drops back down, giving off the extra energy as a small amount of heat. An example
is corundum with the coupled substitution. The simplified chemical equation representing various oxidation
states can be given as:

Fe2+ + Ti4+ → Fe3+ + Ti3+

This reaction absorbs red photons and gives sapphire its characteristic blue color. In hematite, the
process absorbs all visible photons. Materials that exhibit this property retain their dark color regardless of
how finely they are ground. Materials exhibiting metal to metal charge transfer (MMCT) are also conductors.
MMCT generally shows a strong sloping spectral signature in the range 500-1000 nm. Edge-shared octahedral
geometries generally exhibit MMCT in the range 700-800 nm, while face-shared octahedral complexes exhibit
it is in the range of 800-900 nm. In order for metal-to-metal–charge-transfer (MMCT) to occur, orbital must
overlap so electrons can flight back and forth. Examples of the systems displaying metal to metal charge
transfer are:

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 CHAPTER 8 Electronic Spectra of Transition Metal Complexes: 335

Table 16. The type of transition and their wavenumbers of the absorption peaks for MnO4−.

System Absorption maxima (nm)

Fe2+ → Fe3+ (edge-shared) 700-800

Fe2+ → Fe3+ (face-shared) 800-900

Ti3+ → Ti4+ 600-800

Mn2+ + Ti4+ → Mn3+ + Ti3+ 380-450

The most popular example of inter-valence charge transfer is “Prussian blue”. This compound has
the formula KFe[Fe(CN)6] and shows a very intense blue color owing to the transfer of an electron from Fe2+
to Fe3+. In the crystal structure of Prussian blue, the Fe2+ ions are bonded with N atom while the Fe3+ ions are
bonded with C atom of octahedrally surrounding of CN− ligands. Therefore, the charge transfer takes place
through the cyanide bridge.
 Ligand to Ligand Charge Transfer
The ligand to ligand or inter-ligand charge transfer may be defined as the excitation and subsequent
transfer of an electron from a one ligand orbitals to a neighboring ligand orbital.
The ligand to ligand charge transfer (LLCT) or inter-ligand charge transfer transitions are quite
uncommon and rarely observed. In comparison to the enormous literature on metal-to-ligand and ligand-to-
metal charge transfer, very little has been published on LLCT. In most of the cases, LLCT peaks are difficult
to detect in UV-visible absorption spectra; which can be attributed to the fact that these peaks may be obscured
or hidden under absorption bands of different origins, or they may occur at a position very distinct from those
ordinarily analyzed. The LLCT bands are of low intensity due to the poor overlap between the participating
orbitals. Molecular orbitals with dominant ligand characters may have some amount of metal character also,
and a transition that is labelled as ligand to ligand may in fact also involve the metal to some point. However,
if the LLCT is pure, it would have transition energy that does not change considerably when the metal is
changed. A more specific form of Lred–M–Lox complexes is mixed-valence compounds (ligand-based), which
possesses the same ligand in two different redox states. In this case, the interaction between ligands may yield
a partial or complete electron delocalization between the oxidized and reduced form of the ligands. Therefore,
the LLCT loses its charge-transfer character because now it is occurring between delocalized orbitals.
One of the recent examples of metal complexes involving ligand to ligand charge transfer is
(CuTpAsPh3). The emission and UV-visible absorption spectra of (CuTpAsPh3), contain low-energy bands
(with a band maximum at 16 500 cm−1 in emission and a weak shoulder at about 25000 cm−1 in absorption)
that are not present in the corresponding spectra of the phosphine or amine complexes. The peaks are assigned
to the ligand to ligand charge transfer (LLCT) may have some contribution from the metal.

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Table of Contents
CHAPTER 1 ..................................................................................................................................... 11
Stereochemistry and Bonding in Main Group Compounds: ........................................................ 11
 VSEPR Theory ................................................................................................................................ 11
 dπ–pπ Bonds .................................................................................................................................... 23
 Bent Rule and Energetic of Hybridization....................................................................................... 28
 Problems .......................................................................................................................................... 42
 Bibliography .................................................................................................................................... 43

CHAPTER 2 ..................................................................................................................................... 44
Metal-Ligand Equilibria in Solution:................................................................................................. 44
 Stepwise and Overall Formation Constants and Their Interactions ................................................ 44
 Trends in Stepwise Constants .......................................................................................................... 46

 Factors Affecting Stability of Metal Complexes with Reference to the Nature of Metal Ion and
Ligand .............................................................................................................................................. 49
 Chelate Effect and Its Thermodynamic Origin................................................................................ 56
 Determination of Binary Formation Constants by pH-metry and Spectrophotometry .................... 63
 Problems .......................................................................................................................................... 68
 Bibliography .................................................................................................................................... 69

CHAPTER 3 ..................................................................................................................................... 70
Reaction Mechanism of Transition Metal Complexes – I: ............................................................ 70
 Inert and Labile Complexes............................................................................................................. 70
 Mechanisms for Ligand Replacement Reactions ............................................................................ 77
 Formation of Complexes from Aquo Ions ....................................................................................... 82
 Ligand Displacement Reactions in Octahedral Complexes- Acid Hydrolysis, Base Hydrolysis .... 86
 Racemization of Tris Chelate Complexes ....................................................................................... 89
 Electrophilic Attack on Ligands ...................................................................................................... 92
 Problems .......................................................................................................................................... 94
 Bibliography .................................................................................................................................... 95
CHAPTER 4 ..................................................................................................................................... 96
Reaction Mechanism of Transition Metal Complexes – II:...................................................... 96
 Mechanism of Ligand Displacement Reactions in Square Planar Complexes ................................ 96
 The Trans Effect .............................................................................................................................. 98
 Theories of Trans Effect ................................................................................................................ 103

 Mechanism of Electron Transfer Reactions – Types; Outer Sphere Electron Transfer Mechanism and
Inner Sphere Electron Transfer Mechanism .................................................................................. 106
 Electron Exchange ......................................................................................................................... 117
 Problems ........................................................................................................................................ 121
 Bibliography .................................................................................................................................. 122

CHAPTER 5 ................................................................................................................................... 123

Isopoly and Heteropoly Acids and Salts: ........................................................................................ 123
 Isopoly and Heteropoly Acids and Salts of Mo and W: Structures of Isopoly and Heteropoly
Anions ............................................................................................................................................123
 Problems ........................................................................................................................................ 152
 Bibliography .................................................................................................................................. 153

CHAPTER 6 ................................................................................................................................... 154

Crystal Structures: ............................................................................................................................... 154
 Structures of Some Binary and Ternary Compounds Such as Fluorite, Antifluorite, Rutile, Antirutile,
Crystobalite, Layer Lattices - CdI2, BiI3; ReO3, Mn2O3, Corundum, Pervoskite, Ilmenite and
Calcite.............................................................................................................................................154

 Problems ........................................................................................................................................ 178

 Bibliography .................................................................................................................................. 179

CHAPTER 7 ................................................................................................................................... 180

Metal-Ligand Bonding: ....................................................................................................................... 180
 Limitation of Crystal Field Theory ................................................................................................ 180
 Molecular Orbital Theory – Octahedral, Tetrahedral or Square Planar Complexes...................... 184
 π-Bonding and Molecular Orbital Theory ..................................................................................... 198
 Problems ........................................................................................................................................ 212
 Bibliography .................................................................................................................................. 213
CHAPTER 8 ................................................................................................................................... 214
Electronic Spectra of Transition Metal Complexes: .................................................................... 214
 Spectroscopic Ground States ......................................................................................................... 214
 Correlation and Spin-Orbit Coupling in Free Ions for 1st Series of Transition Metals ................. 243
 Orgel and Tanabe-Sugano Diagrams for Transition Metal Complexes (d1 – d9 States) ................ 248
 Calculation of Dq, B and β Parameters ......................................................................................... 280
 Effect of Distortion on the d-Orbital Energy Levels ..................................................................... 300
 Structural Evidence from Electronic Spectrum ............................................................................. 307
 Jahn-Tellar Effect .......................................................................................................................... 312
 Spectrochemical and Nephelauxetic Series ................................................................................... 324
 Charge Transfer Spectra ................................................................................................................ 328
 Electronic Spectra of Molecular Addition Compounds................................................................. 336
 Problems ........................................................................................................................................ 340
 Bibliography .................................................................................................................................. 341

CHAPTER 9 ................................................................................................................................... 342

Magnetic Properties of Transition Metal Complexes: ................................................................. 342
 Elementary Theory of Magneto-Chemistry ................................................................................... 342
 Guoy’s Method for Determination of Magnetic Susceptibility ..................................................... 351
 Calculation of Magnetic Moments ................................................................................................ 354
 Magnetic Properties of Free Ions ................................................................................................... 359
 Orbital Contribution: Effect of Ligand-Field ................................................................................ 362
 Application of Magneto-Chemistry in Structure Determination ................................................... 370
 Magnetic Exchange Coupling and Spin State Cross Over ............................................................ 375
 Problems ........................................................................................................................................ 384
 Bibliography .................................................................................................................................. 385

CHAPTER 10 ................................................................................................................................. 386

Metal Clusters: ...................................................................................................................................... 386
 Structure and Bonding in Higher Boranes ..................................................................................... 386
 Wade’s Rules ................................................................................................................................. 401
  Carboranes ..................................................................................................................................... 407
 Metal Carbonyl Clusters- Low Nuclearity Carbonyl Clusters....................................................... 412
 Total Electron Count (TEC) .......................................................................................................... 417
 Problems ........................................................................................................................................ 424
 Bibliography .................................................................................................................................. 425

CHAPTER 11 ................................................................................................................................. 426

Metal-Π Complexes: ............................................................................................................................ 426
 Metal Carbonyls: Structure and Bonding ...................................................................................... 426
 Vibrational Spectra of Metal Carbonyls for Bonding and Structure Elucidation .......................... 439
 Important Reactions of Metal Carbonyls....................................................................................... 446

 Preparation, Bonding, Structure and Important Reactions of Transition Metal Nitrosyl, Dinitrogen
and Dioxygen Complexes.............................................................................................................. 450
 Tertiary Phosphine as Ligand ........................................................................................................ 463
 Problems ........................................................................................................................................ 469
 Bibliography .................................................................................................................................. 470

INDEX ............................................................................................................................................. 471