COORDINATION

COMPOUND

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 COORDINATION COMPOUNDS (COMPLEX SALTS)

Molecular/Addition compound :
When two or more simple salts are allowed to chemically combine together in a fixed proportion by weight,
then molecular/addition compounds are formed, depending upon their behaviour in aqueous solution they are
classified into two types of salts named as double salts and complex salts.

Double salts :
Molecular/addition compound in which individual components don’t lose their identity and aqueous solution
gives positive test of all constituent ions is called double salt.

1. FeSO4 + (NH4)2SO4+ 6H2O FeSO4.(NH4)2SO4.6H2O Fe2+(aq) +2 NH+4 (aq)+ 2SO24 – (aq)+ 6H2O
(Simple salt) (Simple salt) Mohr’s salt green colour
(Light green crystals)

2. KCl + MgCl2 + 6H2O KCl.MgCl2.6H2O K+(aq) + Mg2+(aq) + 3Cl–(aq) + 6H2O

Carnallite

3. K2SO4 + Al2(SO4)3 + 24H2O K2SO4.Al2(SO4)3.24H2O

(Simple salt) (Simple salt) Potash Alum (Double salt)
(white crystalline solid)

2K+(aq) + 2Al3+(aq) + 4 SO24 – (aq) + 24H2O ( )

Some important points about Alums :

Empirical formula of Alum : M M(SO4)2.12H2O
Molecular formula of alum : M2SO4.M2(SO4)3.24H2O or M2M2(SO4)4.24H2O
where M = Monovalent cation like NH+4 and all s-block alkali metal cations except Li+ cation.
M = Trivalent cation like Al3+, Fe3+, Cr3+ etc.
Naming of Alums :
K2SO4.Al2(SO4)3.24H2O - Potash Alum
Na2SO4.Al2(SO4)3.24H2O - Soda Alum
(NH4)2SO4.Al2(SO4)3.24H2O - Ammonium Alum
M'2SO4.Fe2(SO4)3.24H2O - Ferric Alum
K2SO4.Fe2(SO4)3.24H2O - Potassium Ferric Alum
Na2SO4.Fe2(SO4)3.24H2O - Sodium Feric Alum
(NH4)2SO4.Fe2(SO4)3.24H2O - Ammonium Ferric Alum
M'2SO4.Cr2(SO4)3.24H2O - Chrome Alum.
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Complex salts :
Molecular Addition Compound in which individual components may lose their identity and its aqueous solution
doesn’t give positive test of all its constituent ions is called complex salt.

1. Formation of Potassium Ferrocyanide K4[Fe(CN)6]

+2

2. Formation of Potassium Ferricyanide ion K3[Fe(CN)6]

f sp 3+ 3+ –
+ 3–
3 3 6 6

3+

Classification of complex salts on the basis of their composition : Complex salts are classified into four types

1. Complexes having simple cation and complex anion.

K+[Ag(CN2)]–, K +3 [Fe(CN)6]3–, K +4 [Fe(CN)6]4–, K +2 [CuCl4]2–

2. Complexes having complex cation and simple anion.

[Cu(NH3)4]2+ SO24 – , [Ag(NH3)2]+Cl–, [Co(H2O)6]2+ Cl2–
2
, [Ni(NH3)6]2+ SO24 –

3. Both cation and anion are complex.

2 2– 2 2– 2 2–
 4   2   4   2   3   2 
Pt(NH3 )4  Pt Cl4  , Pt Cl2 (NH3 )4  Pt Cl 4  , Cr Cl(NH3 )5   Zn Cl4 

4. Neutral or molecular complexes.

[Fe(CO)5]0 , [Ni(CO)4]0 , [Cr(CO)6]0  M(CO)x (Neutral metal carbonyl complexes)

Classification of complex salts on the basis of type of ligands around CMA/ion.

Homoleptic complex  metal surrounds by same type of ligands

K +4 [Fe(CN)6]4–, [Ag(NH3)2]+Cl–, [Co(H2O)6]2+ Cl22 – , [Ni(NH3)6]2+ SO24 –

Heteroleptic complex  metal surrounds by different type of ligands

2 3 2
PtCl2 NH3 4
 , Co H2O 3
NH3 
3
, CrBr NH3 5  , Ni NH3 4
Cl2 

Representation of complex ion :

where M : Central metal atom/ion (usually d-block cations)

L : Surrounding ligands (Lewis base)
x : Total number of surrounding ligands
n ± : (+ve) or (–ve) unit charge on coordination sphere.
Outside region apart from coordination sphere is called ionization sphere.
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Ligand : Electron rich species which can donate one or more electron pairs (.p. or -electron pair) to the vacant
orbital of central metal atom/ion is called ligands.

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 Denticity : Denticity of a ligand represents number of co-ordinate bonds that it can form simultaneously to
same central metal atom/ion.

Bidentate Ligands : Having two donor atoms/coordination sites.

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 2

2 3 3

2
2 2
2

• Symmetrical ligands : Ligands having plane of symmetry (P.O.S.) w.r.t. donor sites and passing through
central metal atom/ion are called symmetrical ligands. e.g. ox , en , dipy , phen , acac.

• Unsymmetrical ligands : Ligands having no plane of symmetry (P.O.S.) w.r.t. donor sites and passing through
central metal atom/ion are called unsymmetrical ligands. e.g. DMG , gly , bcac , pn.
Note : No. of stable rings formed by a polydentate ligand = (denticity) – 1

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Types of Polydentate Ligands

(i) Tridentate Ligand : Having three donor atoms/coordination sites.

(ii) Tetradentate Ligands : Having four donor atoms/coordination sites.

(iii) Pentadentate ligand :

2 2 2 2 2 2 2 2 2 2

(iv) Hexadentate Ligand :

Flexidentate character of EDTA4– at different pH value

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 * EDTA4– always gives octahedron geometry due to six coordinaion sites.

2
–

2 +2
OR
2 –

2
2
–

2–

Ambidentate Ligands :When negative ligands have at least two different donor sites, but at a time of coordination
one donor site is used are called ambidentate ligands with monodentate behaviour. However Ambidentate
ligands having sp2 or sp3 hybridized central atom, can also act as flexidentate ligands.

–
2
–

2–
2 3
2–
2 2
2–
3
2–
2
–

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(III) Classical (Normal) and Nonclassical (-Acid) ligands.

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Co-ordination number (C.N.) of metal cation :
Total number of e– pairs accepted by central metal atom /ion from donor atom of surrounding ligands is called
C.N. of central metal atom/ion. It is also called secondary valency of central metal atom / ion.

Table for Coordination Number of metal cation in a particular oxidn state (Stable oxidn state)
Monovlnt C.N. Divalent C.N. Trivalent C.N. Tetravalent C.N. Other C.N.
Cation Cation Cation Cation Cation

Cu+ 2, 4 Ti2+ 4, 6 Sc3+ 6 Ni4+ 6 Cr6+ 6

Ag+ 2, 4 V2+ 4, 6 Ti3+ 6 Pd4+ 6 Os8+ 6
Au+ 2, 4 Cr2+ 4, 6 V3+ 6 Pt4+ 6 Os6+ 6
Mn2+ 4, 5, 6 Cr3+ 6 Pb4+ 6
Fe2+ 4, 5, 6 Mn3+ 6 Sn4+ 6
Co2+ 4, 6 Fe3+ 6 Mo4+ 6
Ni2+ 4, 5, 6 Co3+ 6
Cu2+ 4, 5, 6(rare) Rh3+ 6
Zn2+ 4(Alys Td),6(H2O) Ir3+ 6
Cd2+ 4, 6 Ru3+ 6
Hg2+ 2, 4 Os3+ 6
Pd2+ 4(Alwys Sq.pl.) Ag3+ 4(Alwys Sq.pl.)
Pt2+ 4(Alwys Sq.pl.) Au3+ 4(Alwys Sq.pl.)
Pb2+ 4, 6 Al3+ 4, 6
Sn2+ 4, 6 Bi3+ 4, 6
Ca2+ 4, 6
Mg2+ 4, 6
Be2+ 4(Alwys Td)

IMPORTANT POINTS
1. NH4+ cation never act as ligand.
2. Metal cation with >+2 (more than +2) oxidation state usually have their stable C.N. = 6 with any ligands.
3. Monodentate ligands having more than one lone pair on donor site can act as bridging ligands except
CO (act as bridge ligand with equal sharing of electron of carbon).

4. Neutral ligands in which two different atoms are having lone pairs, then preferential donor site is less
electronegative atom eg. CO, NO.
5. N2H4 never act as bidentate ligand because it will form unstable three membered ring with central metal

atom/ion eg.

6. Ligands containing carbon and nitrogen atom as donor sites are called strong field ligands (SFL) and rest of
them are considered as weak field ligands (WFL) in spectrochemical series. (Except N3– ion is WFL)
7. Cr3+  Coordination Number (C.N.) = 6
[Cr(NH3)5(SO4)]+ : SO42– act as monodentate ligand.
[Cr(NH3)4(SO4)]+ : SO42– act as bidentate ligand.

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 QUESTIONS FOR PRACTICE–1

Single Choice Questions :

1. Consider the complex [Co(NH3)4CO3]ClO4 , in which coordination number, oxidation number and number of
d-electrons on the metal are respectively
(A) 6, 3, 6 (B) 6, 2, 7 (C) 5, 3, 6 (D) 5, 3, 7

–
2. The comon features among the species CN , CO and NO+ are

(A) Bond order three (B) Isoelectronic

(C) All are -donor and -acceptor (D) All of these

3. The -acid ligand which uses its d-orbital during synergic bonding in its complex compound.
–
(A) CN (B) PR3 (C) NO (D) N2

4. Statement-1 : In N2H4, any one N-atom can coordinate with central Metal cation in a coordination compound.
Statement-2 : N2H4 can also act as ambidentate ligand.
(A) Statement-1 is true, Statement-2 is true and Statement-2 is correct explanation for Statement-1
(B) Statement-1 is true, Statement-2 is true and Statement-2 is NOTcorrect explanation for Statement-1
(C) Statement-1 is true, Statement-2 is false
(D) Statement-1 is false, Statement-2 is true

Single Choice Questions :

5. Which of the following does not act as -acid ligand.

(A) F– (B) O22– (C) N2H4 (D) C2H2

6. Which of the following ligand(s) can act as -acid ligand.

(A) -cyclopentadienyl (B) -Allyl (C) B3N3H6 (D) -cyclopentadienyl

Subjective :

7. Calculate value of “x  y” if x is the total number of  bonds and y is total number of  bonds in both ligands
EDTA and Phenanthrolene respectively.
{EDTA = Ethylene diamine tetraacetate, Phen = 1, 10 – N, N-Phenanthrolene}

8. Consider the following ligands NH2–, acac, OH–, Gly, O2–, Phen, DMG, NO2–, CO32–, Cl–, CH3COO–, en, SO42–.
Then calculate value of "P + Q – R – S"
Here P : Total number of ligands which act as bridging as well as monodentate only.
Q : Total number of flexidentate ligands
R : Total number of symmtrical bidentate ligands
S : Total number of unsymmtrical bidentate ligands

9. Find the number of ligand(s) which is/are classical ligand(s).

CO, NO, C2H4, 3-C3H5–, H–, PH3, N2H4, C5H5–, C6H6

10. Find the number of ligands which may act as  donor as well as  acceptor non-classical ligand.
CO, PH3, PF3, C3H5–, C5H5–, NO, C6H6, CN–.

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 Synergic bonding in metal carbonyl complexes : M(CO)x

Synergic bond in metal carbonyl complexes

Effects of synergic bonding :
In metal carbonyl complexes during synergic bonding metal-ligand bond gets stronger and its bond order
increases (M L B.O. > 1). While within CO ligand carbon-oxygen bond order decreases (CO B.O. < 3)
because already existing -bond gets weaker.

CO bond order CO bond length

(1) Free CO molecule = 3.0 = 1.128 Å
(2) M(CO)x < 3.0 > 1.128 Å
(3) H3B  CO > 3.0 < 1.128 Å

Specific colour of all carbonyl complexes is due to metal to ligand (M  L) charge transfer
phenomenon which occurs through synergic bond.

Synergic bond in Zeise’s salt K[PtCl3(–C2H4)].H2O :

Zeise’s salt is yellow coloured due to charge transfer phenomena. It contains one H2O molecule as water of
crystallization.

K+ 

In Zeise’s Salt : K[PtCl3(2 - C2H4)]

Equivalent (Pt – Cl) Bond Length = 2

Total number of -bonds = 8
Total number of -bonds = 2 (-donation is not counted as it is only shifting of
 e– density of ligand towards CMA/ion).

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Experimental evidence of synergic bonding in metal carbonyl complexexs by IR spectroscopy.

1 k
 CO (wave no.)  cm –1
2c 

where
CO : Stretching frequency (wave no.) of CO ligand (energy required to stretch CO bond).
c : Velocity of light.
k : Force constant of CO ligand.
 : Reduced mass of CO ligand.

Strength of back bond  –ve charge on metal atom

1 1
Strength of back bond    CO bond length.
CO CO bond strength (Bond Energy)

1
Strength of back bond  (M  L) bond strength/energy  M  L Bond length

QUESTIONS FOR PRACTICE–2

Single Choice Questions :
1. In which of the following carbonyl complexes, CO stretching frequency is minimum?
(A) [Cr0(CO)6] (B) [Fe+2(CO)6]2+ (C) [V–1(CO)6]– (D) [Mn+(CO)6]+

2. In isolated state, CO bond length is 1.128 Å. Comment on CO bond length in metal carbonyl complexes.
(A) 1.128 Å (B) 1.115 Å (C) 1.151 Å (D) 1.751 Å

3. In which of the following carbonyl complexes, CO bond strength is maximum.

(A) [Fe0(CO)5] (B) [Mn+1(CO)6]+ (C) [V–(CO)6]– (D) [Cr0(CO)6]0


4. In NO complexes , M  NO back bonding the d-orbital(s) of the metal which participate in bonding with
*-Molecular orbital of NO ligand will be :
(A) d (B) dxz , dyz (C) only dxz (D) dxy , d
x 2 y 2 z2

5. Which of the following complex is having largest C – O bond length

(A) [V(CO)6]¯ (B) [Mn(CO)6]+ (C) [Mn(CO)5]¯ (D) [Ti(CO)]6]2–

6. The Infra-red stretching frequency ( CO ) of given compounds P to S follows the order

(P) Mn(CO)6 (Q) CO (R) H3B  CO (S) [V(CO)6]–

(A) P > R > S > Q (B) S > P > R > Q (C) Q > S > P > R (D) R > Q > P > S

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7. Correctly matched CO (stretching frequencies of CO ligand in cm–1) with their respective complex species, is :

[Cr(CO)6] [Ti(CO)6]2– [Mn(CO)6]+

(A) 1859 2000 2143

(B) 2000 2100 1748

(C) 2184 2100 1748

(D) 2000 1748 2100

8. H.O.M.O. (Highest Occupied Molecular Orbital) of CO molecule is
(A) Non-bonding M.O. with slight antibonding character
(B) Non-bonding M.O. with slight bonding character
(C) Pure non-bonding M.O.
(D) None of these

9. Statement-1 : In Zeise's salt C – C bond order regarding ethylene molecule is less than two.
Statement-2 : Ethylene accepts electron pair from filled d-orbital of Pt2+ into its vacant bonding
M.O.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

One or more than one correct :

10. For the metal-olefin complex (i) [PtCl3(C2H4)]– and (ii) [PtCl3(C2F4)]–, the correct statement is/are
(A) carbon-carbon bond length is same both in (i) and (ii)
(B) carbon-carbon bond length in (i) is smaller compared to that of (ii)
(C) carbon-carbon bond length in (i) is larger compared to that of (ii)
(D) Both complexes are diamagnetic

Comprehension-1 (11 to 15) :

Two important physical evidences supporting the synergic bonding in non-classical complexes are bond
lengths and vibrational spectra. Vibrational spectra is based on the fact that the compression and extension
of a bond may be likened to the behaviour of a spring and obeys Hook's law

1 k
 = cm–1
2c 

where , k = force constant of the bond which is directly proportional to bond strength.
 = Reduced mass of ligand.

 = stretching frequency of the bond

c = velocity of light

11. The carbonyl compound that has least value of  for CO is :

(A) [Mn(CO)6]+ (B) [Mn (dien) (CO)3]+ (C) [Cr(CO)6] (D) [Cr(dien) (CO)3]

12. In which complex, M – C bond order is maximum :

–
(A) [Fe (CO)4]2– (B) [Co(CO)4 ] (C) H[Co(CO)4] (D) [Ni(CO)4]
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13. Which of the following orbital of ligand can participate in back bonding in non-classical complexes.

(A) M.O. (B) All d-orbitals (C) * M.O. (D) All

14. In which of the following complex stretching frequency for CO ligand is least as well as bond energy of
M – C bond is higher.

(A) (dien) Mo(CO)3 (B) (Et3P)3 Mo(CO)3 (C) (F3P)3 Mo(CO)3 (D) (Cl3P)3 Mo(CO)3

15. In which of the following ligand, bond order does not change during synergic bonding in their respective
complexes

(A) CO (B) N2 (C) CH2 = CH2 (D) PEt3

Comprehension-2 (16 to 17)

If in the mixed carbonyl, the other ligand is also pi acceptor, it would compete with the ligang CO for gaining
of d electron density. Higher will be the extent of back donation in CO, leaser will be the stretching vibration
frequency for C—O bond.

16. Select the correct order of M—C bond order in the following molecule and ions :
(A) [Ni(CO)4] > [Co(CO)4]– > [Fe(CO)4]2– (B) [Ni(CO)4] = [Co(CO)4]– = [Fe(CO)4]2–
(C) [Co(CO)4]– > [Fe(CO)4]2– > [Ni(CO)4] (D) [Ni(CO)4] < [Co(CO)4]– < [Fe(CO)4]2–

17. Select the correct order of C—O bond length in the following molecules
(A) [Mo(CO)3 (PF3)3] > [Mo(CO)3 (PCl3)3] > [Mo(CO)3 (P(Me)3)3]
(B) [Mo(CO)3 (P(Me)3)3] > [Mo(CO)3 (PF3)3] > [Mo(CO)3 (PCl3)3]
(C) [Mo(CO)3 (PCl)3)3] > [Mo(CO)3 (P(Me)3)3] > [Mo(CO)3 (PF3)3]
(D) [Mo(CO)3 (PF3)3] < [Mo(CO)3 (PCl3)3] < [Mo(CO)3 (P(Me)3)3]

Comprehension-3 (18 to 19)


Crystallographic evidence for M – CO bonding model describes that greater the extent of M  CO back
bonding, more the C – O bond will be lengthened and M – C bond will be shortened. The  interaction, on the
other hand, will have opposite effect on the C – O bond length because the lone pair on carbon that is utilized
in forming  bond is in a slightly antibonding MO of the carbon monoxide.

18. Which of the following species are correctly matched regarding their CO (stretching frequencies of CO
ligand in cm–1)

 of CO  of CO+  of CO in [V(CO)6]–

(A) 2184 2143 1859

(B) 2143 1859 2184

(C) 1859 2000 2143

(D) 2143 2184 1859

19. For which metal ligand interaction bond order of ligand remains almost same :
(A) M – CN (B) M – CO (C) M – N2 (D) M – PF3

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Effective atomic number (EAN) of central metal atom/ion :

Total number of electrons present on central metal atom (CMA) / ion after accepting electron pairs from
surrounding ligands is called EAN (effective atomic number) of central metal atom/ion.

Sidwick’s Rule of EAN :

According to this rule, when EAN of central metal atom or ion in complex compound is equal to nearest
noble gas configuration, then stability of such complex is more.

Complex compound EAN

K4[Fe+2(CN)6]–4 26 – 2 + 6 × 2 = 36
[Cr0(CO)6] 24 – 0 + 6 × 2 = 36
[Fe0(CO)5] 26 – 0 + 5 × 2 = 36 EAN is equal to nearest noble gas configuration
–
[Co3+ (EDTA)] 27 – 3 + 2 × 6 = 36 following sidwicks rule of EAN
[Co+3(en)3]+3 27 – 3 + 2 × 6 = 36

Complex EAN
K3[Fe3+(CN)6] 26 – 3 + 12 = 35
[Ni+2(DMG)2] 28 – 2 + 2 × 4 = 34
(Rosy red ppt)
[Fe3+(H2O)6]+3 26 – 3 + 12 = 35 Not following sidwicks rule of EAN
K[Pt+2Cl3( – C2H4)]0 78 – 2 + 4 × 2 = 84
(Ziese salt)
V(CO)5 23 – 0 + 5 × 2 = 33

Violation of sidwick’s rule of EAN :

Stability order : K3 [Fe+3(CN)6] > K4[Fe2+(CN)6]

EAN = 35 EAN = 36

In metal carbonyl complexes, when EAN of CMA/ion is either less or more than nearest noble gas
configuration, then they have tendency to achieve nearest noble gas configuration. In this way, such carbonyl
complexes act as oxidant and reductant respectively.

[Mn0(CO)6] (less stable) [Mn+1(CO)6]+ (stable)

EAN = 25 – 0 + 12 = 37 (Acts as Red. Agt.) EAN = 25 – 1 + 6 × 2 = 36

[V0(CO)6]0 (less stable) [V–1(CO)6]– (stable)

EAN = 23 – 0 + 12 = 35 (Acts as Oxd. Agt.) EAN = 23 + 1 + 6 × 2 = 36

Note : In carbonyl complexes, metal may have –ve O.S. (–2, –1) because of stabilisation due to synergic bonding.

–
[Fe0(CO)4]0 (less stable) [Fe–2(CO)6] (stable)

EAN = 26 – 0 + 8 = 34 (Acts as Oxd. Agt.) EAN = 26 + 2 + 8 = 36

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Sandwich compounds :

Cr(6 – C6H6) Fe+2(5 – C5H5)2 (Ferrocene)

EAN = 24 – 0 + 2 × 6 = 36 EAN = 26 – 2 + 2 × 6 = 36
Note : If more than one -electron pairs are involved in coordination in -complexes with central metal
atom/ion then its coordination number is not defined.

Conversion of CO metal carbonyl into metal nitrosyl complexes. (When CO lgds are replaced by NO lgds)

Ex.

* Calculation of EAN of central metal atom in polynuclear carbonyl complexes.

All polynuclear carbonyl complexes have -bonds between metal atoms.
Ex. Mn2(CO)10 or (CO)5Mn Mn(CO)5

2  25  2  10  2  1 (  bond)
EAN of Mn atom = = 36
2

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Ex. Fe2(CO)9 or (CO)3Fe(CO)3Fe(CO)3

26  2  6  2  3  2  1 2
EAN of Fe atom = = 36
2
CO B.O. (terminal) > CO B.O. (bridging), hence CO (terminal) > CO (bridging)

Ex.

Co2(CO)8 exists in two formes as follows

Co2(CO)8 (Non-bridge form) (CO)3Co(CO)2Co(CO)3 (Bridge form)

CO B.O. (terminal) > CO B.O. (bridging), hence CO (terminal) > CO (bridging)

QUESTIONS FOR PRACTICE–3

Single Choice Questions :
1. The effective atomic number of Co(CO)4 is 35. It attain stability by
(A) Oxidation of [Co(CO)4] (B) Reduction of [Co(CO)4]
(C) Dimerisation of [Co(CO)4] (D) By both (B) and (C)

2. If CO ligands are substituted by NO in respective neutral carbonyl compounds then which of the following will
not be correct formula
(A) Fe(CO)3(NO)2 (B) [Cr(–C6H6) (NO)2] (C) Ni(CO)(NO)2 (D) Cr(NO)4

3. EAN of the elements (*) are equal in:

* * * *
(A) N i (CO)4, [ Fe (CN)6]4– (B) [ N i (en)2]2+, [ Fe (H2O)6]2+
* * * *
(C) [ Co (CN)6]3–, [ Fe (CN)6]3– (D) [ N i (en)2]2+, [ Sc (H2O)6]3+
4. Which of the following is an oxidizing agent?
(A) Mn(CO)5 (B) Fe(CO)5 (C) Mn2(CO)10 (D) Fe2(CO)9

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5. Choose the correct option regarding the following complex compound which follows (F) and does not follow
(NF) the sidgwick EAN rule:
(I) [(Ph3P)2PdCl2PdCl2] (II) [NiBrCl(en)] (III) Na4[Fe(CN)5NOS] (IV) Cr(CO)3(NO)2
(I) (II) (III) (IV) (I) (II) (III) (IV)
(A) NF NF NF NF (B) F F NF F
(C) NF NF F F (D) NF NF F NF

6. Oxidation number of Cr in the following complex is

(A) 3 (B) 6 (C) 4 (D) 5

7. In carbonyl complex [Fe(CO)4]2–, if maximum number of CO ligands are substituted by NO, then its correct
formula is
(A) [Fe(CO)(NO)2]2– (B) [Fe(NO)3]2– (C) [Fe(NO)3] (D) [Fe(CO)(NO)2]–

Comprehension (8 to 10)
Sidwick EAN rule says that metal carbonyl complex compound has the tendency to achieve the EAN of 36,
54 and 86 for First, Second and Third transition series elements.

8. Which of the following complex acts as reducing agent based on Sidwick EAN rule.
(A) Mn(CO)5 (B) Mn2(CO)10 (C) Mn(CO)6 (D) [V(CO)6]¯

9. Which of the following complex is following sidwick EAN rule.

(A) [Ag(S2O3)2]3– (when only 'S' atom is the donor atom)
(B) [Cd(CN)4]2– (C) [Pt(en)2]2+ (D) [Mo(– C3H5) Br(NH3)2]°

10. Which of following statement is not correct regarding complex "Ferrocene".

(A) EAN of central atom in ferrocene is not equal to its nearest noble gas
(B) Molecule is having aromatic character
(C) It has sandwich like structure
(D) Two rings act as -donor ligand.
Match the column :
11. Column-I Column-II
(A) Mn(CO)5 (P) Oxidizing character
(B) Fe(CO)5 (Q) Reducing character
(C) Co(CO)4 (R) Synergic bonding
(D) Mn(CO)6 (S) Stabilized by dimerization
(T) Doesnot follow Sidgwick rule of E.A.N.
Subjective :
NO
12. M(CO) x (NO)y   M(NO) z
– CO

Where EAN of metal (M) in both product and reactant is same and it is 54. Then calculate value of (x + y – z).
(where x, y and z are natural numbers and M belong to 6th group according to long form of periodic table)

13. Consider the following carbonyl complex compounds.

(i) Mo(CO)x (ii) Hy [Cr (CO)5]
Then calculate value of |x – y|.

14. Consider the following two complex ions : (I) [Co(en)3]n+ (II) [Rh(EDTA)]m–
If both complex ions follow Sidwick's rule of EAN, then calculate the value of expression (n + m)2.
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 RULES FOR IUPAC NAMING OF COMPLEX COMPOUNDS
1. In IUPAC naming of complex compound positive (cationic) part is named first, whether it is simple or complex
followed by naming of negative (anionic) part.
2. In IUPAC naming of complex ion, ligands are named first according to alphabetical order of their names
followed by naming of central metal atom / ion.
3. When there are several monodentate ligands of the same type, then prefix di, tri, tetra, penta, hexa etc. are
provided to the ligands. If monodentate ligand’s name already contain any of these prefix then to avoid
confusion, ‘bis’, ‘tris’, ‘tetrakis’ ‘pentakis’ are used instead of di, tri, tetra, penta etc. and ligand’s name is
placed in parenthesis. Bis, tris prefix is also provided to chelating ligands forming stable 5/6 membered ring
with central metal atom/ion and also with -acid ligands which can be involved in -donation with central
metal atom/ion.
4. Negative ligands have suffix — o,
Positive ligands have suffix — ium,
Neutral ligands have no specific suffix.

But negative organic ligands having '–yl' suffix of hydrocarbon origin are not replaced by '-o'

CH3– – Methyl – Cyclopentadienyl

C2H5– – Ethyl

5. Usually common names are provided to the neutral ligands

except NH3(Ammine), H2O(Aqua/Aquo), CO(Carbonyl), NO(Nitrosyl),

eg. N2(Dinitrogen), O2(Dioxygen), PH3(Phosphene), PMe3(Trimethyl phosphene), PPh3(Triphenyl phosphene),

N2H4(Hydrazine), MeNH2(Methyl amine), EtNH2(Ethyl amine), Me2O(Dimethyl ether),
Me2S(Dimethyl thioether), C6H6(Benzene), C5H5N(Pyridine)

6. In IUPAC naming of complex anion, central metal atom has suffix ‘–ate’ along with its latin or english name
but in case of complex cation/complex neutral molecule central metal atom has no specific suffix with its
common english name.
Metal in complex anion – ium  + ate
Cr Chromate
Pd Palladate
Os Osmate
Ir Iridate
Usually latin names are used for those metals whose symbol is derived from corresponding latin names,
Cu(Cuprum); Fe(Ferrum); Ag(Argentum); Na(Natrium); Au(Aurum); K(Kalium); Sn(Stannum); Pb(Plumbum)
Except : Hg(Mercury); Sb(Antimony); W(Tungsten).
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7. Oxidation state of central metal atom/ion is represented by roman numerals including zero immediate after
metal’s name in parenthesis.

8. In case of polynuclear/bridging complex compound,  - prefix is provided to bridging ligand when it is coordinated
with two metal atoms/ion. When bridinging ligand is coordinated with more than two metal atoms, then prefix
3, 4, .........etc. are provided to the bridging ligands.
IUPAC naming of complex compounds :
(1) K4[Fe(CN)6]  Potassium hexacyanido ferrate(II)
(2) [Cu2+(NH3)4]2+ SO 2–
4 (Switzer’s reagent)  Tetraamminecopper(II) sulphate
(3) K+[Ag+(CN)2]  Potassium dicyanidoargentate(I)
1
(4) K 3
[Cu+1(CN)4]–3  Potassium tetracyanidocuprate(I)
4 2 –1
(5) [Pt Cl2 (NH3 )4 ] 2 [Pt Cl4 ] –2  Tetraaminedichloridoplatinum(IV) tetrachloridoplatinate(II).
3
(6) [Cr(acac)–1
3 ]
0  Tris(acetylacetonato)chromium(III)
2 –1
(7) [Ni(DMG)2 ]0  (Rosy red ppt)  Bis(dimethylglyoximato)nickel(II)
(8) [Co+3(EDTA)–4]–  Ethylenediaminetetraacetatocobaltate(III) ion
0
(9) Cr(CO)6  hexacarbonylchromium(0)
(10) Fe(CO)5  Pentacarbonyliron(0)
(11) Fe+2(5 – C5H5)2 (Ferrocene)  bis(5 – cyclopentadienyl)iron(II)
(12) Cr0(-C6H6)2  bis(6-benzene)chromium(0)
3 –1
(13) [Cr Cl2 (H2 O)4 ]Cl.2H2O  tetraaquadichloridochromium(III) chloride-2-water.
or tetraaquadichloridochromium(III) chloride dihydrate.
3
(14) H+1 [AuCl4 ] –1 (complex acid)  tetrachloridoauric (III) acid
4
(15) H2 [Pt Cl6 ] (complex acid)  hexachloridoplatinic(IV) acid.
2 1
(16) Na22 [Fe(CN)5– (NO)]–2 (Sodium Nitroprusside)  Sodiumpentacyanidonitrosoniumferrate(II)
Note : Sodium Nitroprusside is used for specific test of S2– ion by following reaction.
2 –1 –1
Na2S + Na2[Fe2+(CN)5(NO)]  Na4 [Fe(CN)5 (NOS)] (Purple colour compound)
(Sodium Nitroprusside) Sodium pentacyanidothionitrito–N-ferrate(II)
1
(17) [Fe 1 (H2 O)5 (NO)]SO –2
4
(Brown ring complex)  Pentaaquanitrosyliumiron(I) sulphate
Note : NO is present as positive ligand in both sodium nitroprusside (expt = 0 B.M.) & Brown ring complex
(expt = 15 B.M.)

(18) [Ti(-C5H5)2 (-C5H5)2]  Bis(5-cyclopentadienyl)bis(cyclopentadienyl)titanium(IV)

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 As per old convention complex is written as
[M(–ve ligand) (neutral ligand) (+ve ligand)]n±

As per new convention ligands are written in alphabetical order

[M (ligands are arranged in alphabetical order)]n±
6 –1 –2 –1/0/  2 0
(19) K 2 [Cr(CN)2 (O)2 ( O 2 )(NH3 )]2– (Old convention) Potassium amminedicyanidodioxidoperoxidochromate(VI)

3 –2 –1/ –2 0 0
(20) K 2 [Co(O)2 ( O2 )(NH3 )(O 2 )2 ]2 –(Oldconvention)Potassiumamminebis(dioxygen)dioxidosuperoxidocobaltate(III)

6
K 2 [Cr(NH3 )(CN)2 (O)2 (O2 )]2– (New convention) Potassium amminedicyanidodioxidoperoxidochromate(VI)

3
K 2 [Co(NH3 )(O2 )2 (O)2 (O 2 )]2– (New convention)Potassiumamminebis(dioxygen)dioxidosuperoxidocobaltate(III)

IUPAC naming of bridging/polynuclear complex compounds :

(1) Tetraamminechromium(III)--amido--superoxidotetraamminechromium(III) ion.

(2) -amido--superoxido octaammine dichromium(III) ion.
(3) -amido--superoxido bis{tetraamminechromium(III)} ion.

3+ 3+

2 2

(1) bis(ethylenediamine)cobalt(III)di--hydroxidobis(ethylenediamine)cobalt(III)ion.
(2) di--hydroxido tetrakis(ethylenediamine)dicobalt(III)ion
(3) di--hydroxido bis{bis(ethylenediamine)cobalt(III)}ion
(4) bis{-hydroxidobis(ethylenediamine)cobalt(III)}ion

Note : Adjacent donor site of chelating ligand always occupy adjacent position of geometry.

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Text Example - 1 : I.U.P.A.C. name of the following complex Compounds :
1. K2[HgI4]  Potassium tetraiodidomercurate (II)
2. LiAlH4  Lithium tetrahydridoaluminate (III)
3. K3[Fe(CN)6]  Potassium hexacyanidoferrate (III)
4. K2[Pt Cl6]  Potassium hexachloridoplatinate (IV)
5. [PtCl2(NH3)2]  Diamminedichloridoplatinum (II)
6. [Co(NH3)6]Cl3  Hexaamminecobalt (III) chloride
7. [Fe(en)3]Cl3  Tris (ethylenediamine) iron (III) chloride
8. K3[Ir(C2O4)3]  Potassium trisoxalatoiridate (III)
9. [Co(NCS)(NH3)5]Cl2  Pentaammineisothiocyanato cobalt (III) chloride
Pentaamminethiocyanato–N–cobalt (III) chloride
10. [CoBr(ONO)(en)2]+1  Bromidobis(ethylenediamine) nitrito-O cobalt (III) ion
11. K2[Mo(CN)6]  Potassium hexacyanidomolybdate (IV)
12. [CoI(NH3)5]SO4  Pentaammineiodidocobalt (III) sulphate
13. [Co(NH3)6] [Co(ONO)6]  Hexaammine cobalt (III) hexanitrito–Ocobaltate (III)
14. (NH4)2[Pt(SCN)6]  Ammonium hexathiocyanato–S platinate (IV)
15. [Co(NO2)3(NH3)3]  Triamminetrinitrito-N-cobalt (III)
16. (NH4)3[Cr(NCS)6]  Ammonium hexaisothiocyanatochromate (III)
17. [Pt(NH3)4][PtCl4]  Tetraammine Platinum (II) tetrachloridoplatinate (II)
18. (NH4)4[Mo(CN)8]  Ammonium octacyanidomolybdate (IV)
19. [FeF6]3 –  Hexafluoridoferrate (III) ion
20. [CoCO3(NH3)5]Cl  Pentaamminecarbonatocobalt (III) chloride
21. K3[Fe(NH2)6]  Potassium hexaamidoferrate (III)
22. [PtCl3(SnCl3)]2–  Trichlorido trichlorostannitoplatinate(II)ion
23. Na3[Co(NO2)6]  Sodium hexanitrito–N cobaltate(III)
24. [PtCl4(NH3)2]  Diamminetetrachloridoplatinum (IV)
25. [PtCl2(NH3)4] [PtCl4]  Tetraamminedichloridoplatinum (IV) tetrachloridoplatinate(II)
26. [PdI2(ONO)2(H2O)2]  Diaquadiiodidodinitrito–O palladium (IV)
27. [CoCl(ONO)(en)2]  Chlorobis(ethylenediamine) nitrito–O cobalt (II)
28. [CoCl2(en)2]2SO4  Dichloridobis (ethylenediamine) cobalt (III) sulphate
29. [Cr(CO)5(PPh3)]  Pentacarbonyltriphenylphosphinechromium (O)
30. Na2[Ni(EDTA)]  Sodium ethylenediaminetetraacetatonickelate (II)

31.  Tetraammine cobalt (III) –amido –superoxido tetraammine cobalt (III) ion

OR –amido –superoxido bis {tetraammine cobalt (III)} ion

32. [Be4O(CH3COO)6]  Hexa –– acetato–4 – oxido –tetra beryllium(II)
33. [CuCl(H2O)4]Cl  Tetraquachloridocopper (II) chloride
34. [CoBr(H2O)(NH3)4](NO3)2  Tetraammineaquabromocobalt (III) nitrate
35. Na[B(NO3)4]  Sodium tetranitratoborate (III)
36. [Zn4O(CH3COO)6]  Hexa--acetato-4-oxido-tetrazinc (II)
37. [(C6H5)3PCl Pd Cl2 PdCl(C6H5)3P]
 Chlorotriphenyl phosphene palladium (II) di--chloridochlorido triphenyl phosphene palladium (II)
 di--chloridodichloridobis (triphenylphosphene) di palladium (II)
 di--chloridobis{chloridotriphenyl phosphene palladium (II)}
 bis {–chlorido chloridotriphenyl phosphene palladium (II)}
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38. H2[PtCl6]  Hexacloro platinic (IV) acid
39. [(Cl3Sn)2RhCl2Rh(SnCl3)2] 4— 
IV
SnCl2 + Cl–  SnCl3–
Stannous chloride trichlorostannito
 Bis(trichlorostannito) rhodate (I) di –chlorido bis(trichlorostannito) rhodate(I) ion
 Di––chloridotetrakis(trichlorostannito) dirhodate(I) ion
 Di––chlorido bis{bis(trichlorostannito) rhodate (I)}ion
40. Fe(CO)5  Pentacarbonyl iron (O)
41. Co2(CO)8  Octacarbonyl dicobalt (O)
42. K2[Cd(CN)4]  Potassium tetracyanidocadmate (II)
43. [CrCl2(H2O)4]Cl  Tetraaquodichloridochromium (III) chloride
44. Co[Hg(SCN)4]  Cobalt(II)tetrathiocyanato–S Mercurate(II)
45. [Ag(NH3)2]Cl  Diammine silver (I) chloride
46. K[SbCl5(C6H5)]  Potassium pentachloridophenylantimonate (V)
47. [RuBr2(NH3)4]NO3  Tetraamminedibromoruthenium (III) nitrate
48. [CoCl(NO3)(NH3)4] [Au(CN)2]  Tetraamminechloridonitratocobalt (III) dicyanidoaurate (I)
49. [PtCl(NO2)(en)(NH3)2] Cl2  Diamminechloridoethylenediaminenitrito–N platinum (IV) chloride
50. [Ni(CN)4]2—  Tetracyanidonickelate (II) ion
51. [(NH3)5Cr-OH-Cr(NH3)5]Cl5
 Pentaammine chromium (III) –hydroxo pentaammine chromium (III) chloride
 –hydroxo bis {pentaammine chromium (III)}chloride

52. [Br2Pt(SMe2)2PtBr2] 

(Me2O  dimethyl ether/ Me2S Dimethyl thioehter)

 Dibromoplatinum (II) bis(-dimethyl thioether) dibromoplatinum (II)
 Bis{-dimethylthioether dibromo platinum (II)}
 bis(-dimethyl thioether) tetrabromo diplatinum (II)
53. [PtCl2(Et3P)2]  Dichloridobis (triethylphosphine) platinum (II)
54. [CuCl2(Et2NH)2]  Dichloridobis (diethylamine) copper (II)
55. [CoCl2(en)2]Cl  Dichloridobis (ethylenediamine) cobalt (III) chloride
56. K[PtCl3(C2H4)]  Potassium trichlorido-2-ethylene platinate (II)
57. K2[OsCl5N]  Potassium pentachloridonitridoosmate (VI)
58. Na3[Ag(S2O3)2]  Sodium bis(thiosulphato)argentate (I)
59. Na2[Fe(CN)5(NO)]  Sodium pentacyanidonitrosonium ferrate (II)
[NO in +1 state proved by magnetic moment]
60. K3[Fe(CN)5(CO)]  Potassium carbonyl pentacyanidoferrate (II)

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Text Example - 2 : I.U.P.A.C. name of the following complex Compounds :
1. [ Ni (CO ) 2 (PPh 3 ) 2 ]  Dicarbonyl bis(triphenylphosphine) nickel (O)
2. [(en)2Co(NH2)(OH)Co(en)2]4+  Bis(ethylenediamine) cobalt(III) –amido –hydroxo
bis(ethylenediamine) cobalt(III) ion
3. [(CO)3Fe(CO)3Fe(CO)3]  Tri--carbonyl–bis(tricarbonyl iron (O))
4. [(NH3)5CrOHCr(NH3)4(H2O)]5+  Pentaammine chromium (III) –hydroxotetraammine aquo
chromium(III) ion
5. [CoN3(NH3)5]SO4  Pentaammineazidocobalt (III) sulphate
6. [Co(NH2)2(NH3)4]OC2H5  Diamidotetraamminecobalt(III) ethoxide
7. [Pt(Cl)(NO2)(NH3)4]SO4  Tetraamminechloronitrito–N platinum (IV) sulphate
8. [CrCl2(H2O)4]Cl  Tetraaquodichlorochromium (III) chloride
9. [Ru(N3)(NH3)5]Cl2  Pentaammineazidoruthenium(III) chloride
10. [CoCl3(NH3)3]  Triamminetrichlorocobalt(III)
11. [PtCl4(NH3)2]  Diamminetetrachloroplatinum (IV)
12. [CrCl(H2O)5]Cl2  Pentaaquachlorochromium(III) chloride
13. Ti(-c5H5)2(-C5H5)2  Bis(cyclopentadienyl) bis 5-cyclopentadienyl titanium (IV)

14. Mo(-C3H5)(-C5H5)(CO)3  Allyl tricarbonyl- 5 – cyclopentadienyl molybdum (II)

CH2=CH–CH2(–) allyl

15. Mn(-C5H5)(CO)3  Tricarbonyl- 5 – cyclopentadienyl manganese (I)

16. Cr(C6H6)(CO)3  6 –benzene tricarbonyl chromium (O)

17. Fe(CO)2(-C5H5)(-C5H5)  Dicarbonyl- 5 –cyclopentadienyl cyclopentadienyl iron (II)

18. Cr(C6H6)2  Bis ( 6 –benzene) chromium (O)

19. Fe(-C5H5)2  Bis ( 5 –cyclopentadienyl) iron (II)

20. Mn(CO)5(-C3H5) or Mn(CO)5(–CH2–CH=CH2)  Allyl pentacarbonyl manganese (I)

21. Co(CO)3(-C3H5)  3 –allyl tricarbonylcobalt (I)

22. Fe(   C4H4 )(CO)3  tricarbonyl-4-cyclobutadiene iron (O)
23. [PtCl2(NH3)(C2H4)]  Amminedichloro (2 – ethylene) platinum (II)
24. Ni(CO)4  Tetracarbonylnickel (O)
25. Mn2(CO)10  Decacarbonyl dimanganese (O)
26. [Cu(NH3)4][PtCl4]  Tetraaminecopper (II) tetrachloro platinate (II)
27. [W(en)3]Cl3  Tris (ethylenediamine) tungston (III)chloride
28. K3[Co(NCS)6]  Potassium hexathiocyanato–N cobaltate (III)
29. [Pt(NH3)4][Cr(NCS)(NO2)2(NH3)2Py]  Tetrammine platinum (II) diammine dinitrito-N
pyridine thiocyanato-N chromate (I)
30. K3[Co(C2O4)2Cl2]  Potassium dichlorobis(oxalato)cobaltate (III)

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31.  Tetraamine cobalt (III) di––hydroxo bis (ethylenediamine) cobalt

(III) chloride {III way is not applicable}

32. Na2[Pt(CN)2I(NO2)]  Sodium dicyanidoiodidonitrito-N-platinate (II)
33. [Ru(PPh3)3Cl3]  Trichlorotris(triphenylphosphine)ruthenium(III)
34. K2[Co(N3)4]  Potassium tetraazidocobaltate (II)
35. [NiCl2(Ph3P)2]  Dichlorobis(triphenylphosphine) nickel (II)
36. [Cr(acac)3]  Tris(acetylacetanato) chromium (III)
37. [IrCl(CO)(Ph3P)2]  Carbonylchlorobis(triphenylphosphine) iridium (I)
38. [Co(NCS)(NH3)5]Cl2  Pentaammine thiocyanato–N cobalt (III) chloride
39. [Pt(C5H5N)4] [PtCl4]  Tetrapyridine platinum (II) tetrachloroplatinate (II)
40. [CrCl(ONO)(NH3)4] NO3  Tetraammine chloronitrito-O-chromium (III) nitrate
41. [Co(NH3)6][CuCl5]  Hexaamminecobalt (III) pentachlorocuprate (II)
42. [Ca(EDTA)]2—  Ethylenediaminetetraacetato calcate (II) ion
43. [Fe(H2O)5(NO)]SO4  Pentaaquanitrosonium iron (I) sulphate
[brown ring complex is unstable]
44. K4[Ni(CN)4]  Potassium tetracyanidonickelate (O)
45. [Al(OH)(H2O)5]SO4  Pentaaquohydroxoaluminium (III) sulphate
46. [VBr2(H2O)(NH3)2]Br  Diammineaquodibromovanadium (III) bromide
47. Na[Co(CO)4]  Sodium tetracarbonylcobaltate (–I)
48. Fe4[Fe(CN)6]3  Iron (III) hexacyanidoferrate (II)
49. Fe3[Fe(CN)6]2  Iron (II) hexacyanidoferrate (III)
50. [Cr(en)3] [Ni(CN)5]  Tris (ethylenediamine) chromium (III) pentacyanido nickelate (II)
51. [(NH3)4CoNH2NO2Co(NH3)4](NO3)4 –amido –nitro bis {tetraammine cobalt (III)} nitrate
 Tetraammine cobalt (III) –amido –nitro tetraammine
cobalt (III) nitrate
 –amido –nitro–octamminedicobalt (III) nitrate
52. K[B(C2H5)4]  Potassium tetraethyl borate (III)
53. [PtBr(NH3)3] NO3  Triamminebromoplatinum (II) nitrate
54. trans-[PtCl2(NH3)2]  Trans–diammine dichloroplatinum (II)
55. [RhCl(PPh3)3]  Chlorotris (triphenylphosphine) rhodium (I)
56. [Ni(dmg)2]  Bis (dimethylglyoximato) nickel (II)
57. [Co(NH3)6][Cr(CN)6]  Hexaamminecobalt (III) hexacyanidochromate (III)
58. Ni(–C4H4)2  bis (4- cyclobutadiene) nickel (0)
59. [CoCl(NCS)(NH3)4]+  Tetraamminechlorothiocyanato–N cobalt (III) ion
60. [PtCl4(en)]  Tetrachloroethylenediamine platinum (IV)
61. [CoBrCl(en)(NH3)2] NO3  Diamminebromochloroethylenediamine cobalt (III) nitrate

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 QUESTIONS FOR PRACTICE–4
Single Choice Questions :
1. Which of the following is correct IUPAC name of any complex compound.
(A) Tris (acetyl acetonato) iron (III) chloride
(B) Hexachloridoplatinum (IV) tetraammine dicyanido platinate (IV)
(C) Ammine bromidochlorido methylamine platinum (II)
(D) Cis dichlorido (ethylenediamine) platinum (II)

2. Correct IUPAC name of [Pd(NO3)2(en)2]3 [Cr(CN)6]2 is :

(A) Dinitratobis(ethylenediamine)palladium(IV)hexacyanidochromate(III)
(B) Bis(ethylenediamine)dinitratopalladium(IV)hexacyanidochromate(III)
(C) Bis(ethylenediamine)dinitrato-N-palladium(IV) hexacyanido chromate(III)
(D) Bis(ethylenediamine)dinitratopalladium(II)hexacyanido chromate(III)

3. Correct IUPAC name of complex compound [Co(NCS) (NH3)5] [Zn(CN)4]

(A) Pentaamminethiocyanato-N-cobalt (III) tetracyanidozinc(II).
(B) Pentaamminethiocyanato-S-cobalt (III) tetracyanidozincate(II).
(C) Pentaamminethiocyanato-N-cobalt(II) tetracyanidozincate(II).
(D) Pentaamminethiocyanato-N-cobalt(III) tetracyanidozincate(II).

One or more than one correct :

4. Find out correct I.U.P.A.C. name of complex compound
(A) Pentaamminecyanidochromium(II)hexanitrito-N-irridate(III)
(B) Triamminetricyanidochromium(III)hexanitrito-N-irridate(III)
(C) Hexanitrito-N-irridium(III)pentaamminecyanidochromate(II)
(D) Pentaamminecyanidochromium(III)hexanitrito-N-irridate(III)

5. Select complex(s) with their correct IUPAC name

(A) Fe[Fe(CN)6] Iron (III) hexacyanido ferrate (III)
(B) Fe2[Fe(CN)6] Iron (II) hexacyanido ferrate (II)
(C) Fe3[Fe(CN)6]2 Iron (II) hexacyanido ferrate (III)
(D) Fe4[Fe(CN)6]3 Iron (III) hexacyanido ferrate (II)

Match the column :

6. Column-I Column-II
(A) Hexabromidoplatinate (IV) ion (P) Monodentate ligand is present in complex ion
(B) Potassiumdiamminetetrabromidocobaltate (III) (Q) Negative ligand is present in complex ion
(C) Tris(ethylenediamine) copper (II) (R) Neutral ligand is present in complex ion
sulphate
(D) Hexacarbonylmanganese (I) (S) Central atom of complex ion is a member of
perchlorate 3d (first) transition series
(T) Six coordination number of central atom in
complex ion

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Werner’s Theory of Coordination Compounds :
Werner was the first scientist who tried to explain bonding in complex compounds for that he did some
experiments with various samples of cobalt (III) complexes and expained his theory by giving following
postulates.
(1) In complex compounds, metal cation exhibit two type of valency
(a) Primary valency (oxidation state).
(b) secondary valency (coordination number).
(2) Primary valency is ionizable and secondary valency is non-ionizable.
(3) Every metal cation in complex compound has its fixed secondary valency.
(4) Primary valency is satisfied by –ve ions whereas secondary valency is satisfied either by –ve ions or by
neutral molecules. It means –ve ions may satisfy both type of valencies.
(5) Primary valency has non-directional character whereas secondary valency has directional character. Therefore,
a complex ion has its definite geometry.
3
CoCl3 .6NH3 + AgNO3 solution  3 moles of AgCl

(I)
CoCl3.5NH3 + AgNO3 solution  2 moles of AgCl
(II)
CoCl3.4NH3 + AgNO3 solution  1 mol of AgCl
(III)
CoCl3.3NH3 + AgNO3 solution  No ppt
(IV)
In all above complexes secondary valency of Co3+ is 6

Werner representation

Primary valency Secondary valency

(1) Modern representation = [Co(NH3)6]Cl3

Number of Cl– ions precipitated = 3
Total number of ions = 4 (one complex cation + 3Cl–)

(2) Modern representation = [CoCl(NH3)5]Cl2

Number of Cl– ions precipitated = 2
Total number of ions = 3 (one complex cation + 2Cl–)

– 3 –

3+
–
(3) Modern representation = [CoCl2(NH3)4]Cl
–
3 3 Number of Cl ions precipitated = 1
3
Total number of ions = 2 (one complex cation + 1Cl–)
3 4 3

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(4) Modern representation = [CoCl3(NH3)3]
Number of Cl– ions precipitated = 0
Total number of ions = 0

Order of electrical conductance : 1 > 2 > 3 > 4 (more ions  more conductance)
Complex compound which gives maximum number of total ions in aqueous solution on ionization will have
maximum electrical conductance (charge carrying capacity of ions should be equal).

QUESTIONS FOR PRACTICE–5

Single Choice Questions :
1. A compound has the empirical formula CoCl3·5NH3. When an aqueous solution of this compound is mixed
with excess silver nitrate, 2 mol of AgCl precipitate per mol of compound. On reaction with excess HCl, no

NH4 is detected. Hence, it is:

(A) [Co(NH3)5Cl2]Cl (B) [Co(NH3)5Cl]Cl2
(C) [Co(NH3)5Cl3] (D) [Co(NH3)4Cl2]Cl·NH3
2. Consider the molecular formula of following complexes.
(I) CoCl3.6NH3 (II) CoCl3.5H2O (III) CoCl3.4NH3
If number of coordinated neutral ligands in (I), (II) and (III) complexes are respectively 6, 5 and 4, then primary
valency of metal cation in (I), (II) and (III) respectively are :
(A) 6, 5, 4 (B) 3, 2, 1 (C) 0, 1, 2 (D) 3, 3, 3
3. If excess of AgNO3 solution is added to 100 mL of a 0.024 M solution of dichlorobis (ethylene diamine) cobalt
(III) chloride, how many mol of AgCl be precipitated:
(A) 0.0012 (B) 0.0016 (C) 0.0024 (D) 0.0048
4. Which of the following complexes has the least molar conductivity in the solution?
(A) CoCl3·3NH3 (B) CoCl3·4NH3
(C) CoCl3·5NH3 (D) CoCl3·6NH3

5. Excess AgNO3 solution was added to 100 ml of 0.1 M solution of CoBr3xNH3 and 0.02 moles yellow
coloured precipitate was obtained, then the correct formula of the given complex compound is :
(A) [CoBr2(NH3)4]Br (B) [CoBr(NH3)5]Br2
(C) [Co(NH3)6]Br2 (D) [CoBr2(NH3)4]Br.NH3

Comprehension (6-7)
Addition compounds which do not lose their identity in aqueous solution are called double salts and those
lose their identity in aqeous solution are called complex salts, species which are directly linked with central
metal atom / ion are called ligands. The ligands having two or more donor atoms are called polydentate or
multidentate ligands.
6. Which of the following complex compound is non-ionisable in aqueous solution?
(A) PtCl4 · 3NH3 (B) PtCl4 · 6NH3 (C) PtCl4 · 2NH3 (D) PtCl4 · 4NH3
7. (i) Complex (P) + AgNO3 soln.  White precipitate
(ii) Complex (Q) + BaCl2 soln.  White precipitate
(iii) Complex (R) + Na2SO4 soln.  White precipitate
Pick the most appropriate option
(A) Complex (P) may contain Cl– in coordination sphere but not in ionisation shpere
(B) Complex (Q) may contain Ag+ cation in coordination sphere but not in ionisation shpere
(C) Complex (R) may contain Ba2+ cation in ionisation sphere but not in coordination sphere
(D) Complex (Q) may contain SO42– ion in coordination sphere but not in ionisation shpere

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Valency bond theory (VBT) :
According to VBT surrounding ligands form coordinate bond with the vacant orbital of central metal atom/ion.
These pure vacant orbitals equalise their energy by process of intermixing named as hybridisation.
Type of hybridisation, geometry and magnetic behaviour of complex compound depends upon nature of
ligands. When ligands are arranged in increasing order of their splitting power, then an experimentally
determined series is obtained, named as spectrochemical series.

Splitting power of ligand  electron donating & accepting tendency of ligand.

Spectrochemical series :
I– < Br– < SCN– < Cl– < S2– < NO3– < N3– < F– < OH– < CH3COO– < C2O42– < O2– < H2O (weak field lgds.)
< NCS– CH3CN < EDTA4– < NH3 < Py < en < dipy < Phen < NO2– < PPh3 < CN– < CO...(strong field lgds.)
Note : (i) EDTA4– is strong field ligand due to chelation. (forms stable 5 member ring with central metal atom / ion)
(ii) Strong field ligands (SFL), NCS–, EDTA4–, NH3, Py, en, dipy, phen, NO2–, CN–, CO are also named as low
spin ligands and hyper ligands.
(iii) Weak field ligands (WFL), I– < Br– < SCN– < Cl– < S2– < NO3– < N3– < F– < OH– < CH3COO– < C2O42– <
H2O are also named as high spin ligands and hypo ligands.

Postulates of Valency bond theory (VBT) :

(1) Strong field ligands like CN–/CO will form possible pair of unpaired electrons present in central metal
atom/ions. (SFL  Spin decreases of metal atom/ions).

(2) Weak field ligands like H2O/OH–, will have no effect on electronic configuration of central metal atom/ion.
(WFL  Spin remain constant of metal atom/ions)

(3) Complex compound with zero unpaired electrons is called diamagnetic (repelled by magnetic field) and
complex compound with at least one unpaired electron is called paramagnetic (attracted by magnetic field).

(4) If inner d-orbital are involved in hybridization, then it is named as inner orbital complex and when d-orbitals of
outer shell are involved in hybridization, then it is named as outer orbital complex (inner & outer term is
defined only w.r.t d-orbital).

(5)

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