COMPLEX COMPOUNDS

Differences between Double salt and Complex salt:

 A double salt completely dissociates into its corresponding ions in aqueous solution, where as a complex
compound does not dissociate completely into ions
 Double salt is unstable in aqueous solution and in complex salt the coordination sphere remains intact and
stable.
Important Terminology:
Coordination entity or coordination sphere:
It constitutes of central metal atom surrounded by atoms or groups or ions bonded by coordinate covalent
bonds, represented in a square bracket. Ex: [Fe(CN)6]4-, [Ni(CO)4]
Central atom:
The metal atom that makes a dative bond with a fixed number of atoms or groups / ions
Ligands:
The group / ion which makes a dative bond with the central atom in a coordination sphere.
Coordination number:
It is the number of dative bonds or coordinate bonds around central atom with which Ligands are linked.
Ex: [Fe(CN)6]4-C.N= 6, [Ni(CO)4] C.N = 4, [Cr(en)3]3+
C.N = 6

Oxidation state:
It is the charge carried by the central metal, which is represented by the roman number.
Chelation:
It is the formed by the complexes having at least one Bidentate ligand forming a cyclic ring in its structure.
Ex: [Cr(en)3]3+, [Ag(C2O4)2]2-
 Types of Complexes:
Anionic Complex Cationic Complex Neutral Complex
Coordination sphere has Coordination sphere has Coordination sphere is
negative charge positive charge neutral
Ex: [Ag(C2O4)2]2-, Ex: [Cr(en)3]3+, [Co(NH3)6]3+, Ex: [Ni(CO)4], [Ni(NH3)4],
[Fe(CN)6]4-,

Types of Ligands:
Positive Negative Neutral
Ex: NO+, X+, Ex: CN-, X-, C2O42-, NC-, Ex: NH3, CO, H2O, en,

Denticity:
It is the number of dative bonds with which the ligand holds the central metal.
Monodentate ligand:
Ligand holds the central metal with one dative bond.
Ex: CN-, NH3, H2O etc.,
Bidentate ligand:
Ligand holds the central metal with two dative bonds.
Ex: Ethylene diammine (en), Oxalate C2O42-, SO42-, CO32-, Trimethylenediamine, acetylacetonato
(acac), Glycinato , BiPyridine (Bipy) etc.,
 (CH3-C=N-OH)2 –DMG Detection test of Ni2+ Pink coloured complex
Tridentate ligand:
Ligand that holds the central metal with three dative bonds.
Ex: Terpyridyl, Bisethylene Triammine etc.,

Hexadentate ligand:
Ligand holds the central metal with six dative bonds.
Ex: EDTA Ethylene Diammine Tetra Acetate ion.

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PREVIOUS YEAR QUESTIONS:
1) The following ligand is:
(JEE 2019)

(1) Tetradentate (2) Tridentate (3) Bidentate (4) Hexadentate

ANS: (1)
2) The maximum possible denticities of a ligand given below towards a common transition and inner-
transition metal ion, respectively, are:
(JEE 2019)
 (1) 6 and 8 (2) 8 and 6 (3) 8 and 8 (4) 6 and 6
ANS: (1)
3) The coordination numbers of Co and Al in [Co(Cl)(en)2]Cl and K3[AI(C2O4)3], respectively, are
(JEE 2019)
(en = ethane-1, 2-diamine)
(1) 3 and 3 (2) 5 and 3 (3) 5 and 6 (4) 6 and 6
ANS: (3)
4) The coordination number of Th in K4[Th(C2O4]4(OH2)2] is :-
(JEE 2019)
(1) 6 (2) 10 (3) 14 (4) 8
ANS: (2)
Rules for writing Nomenclature:
 First the cation should be named followed by anion in a complex, if the coordination sphere is cation or
an anion the ligand should be named first followed by central metal
 Number of ligands in a coordination sphere should be given prefix Bi-2, tri-3, Tetra-4, penta-5 and Hexa -
6
 If the ligand has di or tri in its name then Bis, Tris and Tetrakis are prefixes respectively for 2,3, & 4
ligands
 If the complex is anionic complex then the central metal should have a suffix- ate followed by its
oxidation state in roman number (0)
 Negative ligands should be named with suffix-O and multiple ligands are to named in alphabetical order
 For the Bridge complexes, bridging ligands between two metal ions have the prefix ‘µ’

[Be4O(CH3COO)6] Hexa -µ- acetetato (O,OI) -µ- oxido- Beryllium (II)

 Some Examples of Complexes:
[Ni(CO)4] => TetraCarbonyl Nickel (0)
[NiCl4]2- => TetraChloridoNickelate (II) ion
2-
[Ni(CN)4] => TetracyanoNickelate (II) ion
[Cr(NH3)6]Cl3 => TetraAmmineChromium (III) Chloride
Na3[CoF6] => Sodium HexaFluoridoCobalt (III)

Nomenclature of different types of complexes:

 ----------------------------------------------------------------------------------------------------------------------------
PREVIOUS YEAR QUESTIONS:
1) The IUPAC name of the complex [Pt(NH3)2Cl(NH2CH3)]Cl is:
(JEE 2020)
a) Diamminechloridomethylamineplatinum(II) chloride
b) Chloridomethanaminediammineplatinum(II) chloride
c) Diamminechloridomethylamineplatinate(II) chloride
d) None of these
Ans: (a)

Isomerism:
Different complexes having same molecular formula but different structural formula are called isomers and
the phenomenon is isomerism.
Types of isomerism:

Ionisation Isomerism:
Different complexes having same molecular formula but different structural formula as the ions get
exchanged within and outside the coordination sphere of the complexes.

Coordination Isomerism:
Different double complexes having same molecular formula but different structural formula due to the
exchange of central metal between the double complexes.

Solvate or Hydrate Isomerism:

Different complexes having same molecular formula but different structural formula as the water molecules
get exchanged within and outside the coordination sphere

Linkage Isomerism:
Different complexes having same molecular formula but differ in the link between the central metal and
ligand of same type.

Stereo Isomerism:
Different complexes having same molecular formula but different arrangement of atoms in 3D space.
Geometrical Isomerism:
Geometric isomerism is possible for both square planar and octahedral complexes but not tetrahedral
complexes.
a) Cis-Trans Isomerism:
Different complexes having same molecular formula but they have a pair of ligand which are present in
same side are called Cis isomers and present in the opposite side are called trans isomers.
-For Cis-Trans isomerism to be exhibited by complexes they should have atleast one pair of similar
Ligands in the Coordination sphere
b) Facial (Fac) & Meridonial (Mer) Isomerism:
Different complexes having same Molecular formula but the they differ in the arrangement of ligands
present within a Face and outside the Face of a Tetrahedron in a Octahedral Complex.
-Facial and meridonial is exhibited only by Octahedral complexes having atleast one Triplet of
monodentate ligands of same type

Number of Geometrical Isomers in Complexes

Complexes Isomers
Mabcdef 15
Ma2bcde 9
Ma2b2cd 6
Ma2b2c2 5
 Ma3bcd 4
Ma3b2c 3
Ma3b3 2
Ma4b2 2
Ma4bc 2
Ma5b 0
Ma6 0

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PREVIOUS YEAR QUESTIONS:
1) Among the following, which will show geometrical isomerism?
(JEE 2020)
A. [Ni(NH3)5Cl]+ B. [Ni(NH3)4ClBr] C. [Ni(NH3)3Cl]+ D. [Ni(NH3)2(NO2)2]
a. B, D b. A , B c. A , B and C d. A, B, C and D
ANS: (a)
SOL: The complexes of type Ma4bc and Ma2b2 can show geometrical isomerism provided Ma2b2 is
square planar. The compound given in B is Ma4bc type and compound in D is Ma2b2 type also in D, Ni
is surrounded with strong field ligands which will result in dsp 2 hybridisation and hence square planar
geometry.
2) Given the complex: [Co(NH3)4Cl2]. If in this complex, the Cl–Co–Cl bond angle is 90o, then
it is a:
a. Cis-isomer b. Trans-isomers c. Meridional and Trans d. Cis and trans both
ANS: (a) (JEE
2020)
3) The species that can have a trans-isomer is : (en = ethane-1, 2-diamine, ox = oxalate) (JEE
2019)

ANS: (4)

4) The total number of isomers for a square planar complex [M(F)(Cl)(SCN)(NO 2)] is :
(JEE 2019)
(1) 12 (2) 8 (3) 16 (4) 4
ANS: (1)
SOL:

5) Which of the following complexes will show geometrical isomerism? (JEE 2018)
(1) Potassium tris(oxalato)chromate(III) (2) Pentaaquachlorochromium(III)chloride
(3) Aquachlorobis(ethylenediamine)cobalt(II) chloride (4) Potassium amminetrichloroplatinate(II)
ANS: (3)
SOL: [Co(H2O)Cl(en)2]Cl
6) Which of the following complex exhibit facial-meridonial geometrical isomerism?
(JEE 2020)
a. [Pt(NH3)Cl3]- b. [PtCl2(NH3)2] c. [Ni(CO)4] d. [Co(NO2)3(NH3)3]
ANS: (d)
SOL: Facial and meridonial geometrical isomerism is observed only in [MA3B3] type complexes which
is given in option d.

Optical Isomerism:
Different complexes of same molecular formula having non superimposable mirror images are optically
active.
-All cis isomers of Octahedral complexes are optically active

As we can see in the above molecule the trans form cannot have non sumperimposable mirror images.
-The octahedral complexes can have mono dentate or Bi-dentate ligands

Cis Isomers of DiAquaDiOxalatoChromium (III) ion:

Dextro Leavo

Cis Isomers of Tris EthyleneDiammineCobalt(III) ion:

------------------------------------------------------------------------------------------------------------------------------
PREVIOUS YEAR QUESTIONS:
1) For the complex [Ma2b2] if M is sp3 or dsp2 hybridized respectively then the total
number of optical isomers respectively, are:
(JEE 2020)
a. 1, 1 b. 2, 1 c. 0, 0 d. 1, 2
ANS: (c)
SOL: Case 1: If M is sp3 hybridized, the geometry will be tetrahedral. There will be a plane of
symmetry and thus it does not show optical activity.
Case 2: If M is dsp2 hybridized, the geometry will be square planar. Due to the presence of a
plane of symmetry, it does not show optical activity.
 2) The one that will show optical activity is (en = ethane-1,2-diamine) (JEE
2019)

ANS: (3)
SOL: The molecule has no plane or center of symmetry hence optically active.
3) The complex that can show optical activity is: (JEE
2020)
(1) cis−¿ ¿ (2) trans−¿ ¿
3−¿¿
(3) trans−[Cr (Cl2 )(ox )2] (4) cis−¿ ¿
Sol. 1

WERNER’S THEORY OF COMPLEXES:

This theory explains the structure and bonding in coordination compounds, the features are
- In a complex compound central metal exhibits two valencies, primary valency and secondary Valency

----- Represent Primary Valency, ̶ represent Secondary Valency

- Primary Valency is satisfied by negative ions and are ionisable, which is the charge of the central metal.
- Secondary valency is the non-ionisable which can be satisfied by either negative or neutral species, which
is the coordination number of the central metal.
- Secondary valency decides the geometry of the molecule.
Limitations:
-It failed to explain the directional properties of bonds in Complexes
-It couldn’t explain the magnetic behaviour, Colour formation and optical properties of complexes.
-It couldn’t explain the nature of bonding between metal and ligands and give a definite geometry for
complexes having Secondary Valency – 4.

Valence Bond Theory:

-This theory explains the bonding and Geometry of Complexes.
-Orbitals of the central metal undergo hybridisation to give definite Geometry and shape to complexes which
leads to its stability and properties
-Basing on the strength of the ligands, the complexes can be hybridised into Inner orbital and outer orbital
complexes as given in the tabular column.
-Also the magnetic behaviour of the complexes can be interpreted upon the presence of unpaired in the
central metal after making complexes
-Depending on the number of unpaired electrons they classified into Para magnetic, Dia magnetic and
Ferromagnetic with specific Magnetic moments.

HYBRIDISATION SHAPE BOND COMPLEXES

ANGLE
sp Linear 1800 [Ag(NH3)2]+, [Au(CN)2]-
 sp3 Tetrahedral 109028I [Ni(CO)4], [NiCl4]2-, [Cu(NH3)4]2+

dsp2 Square planar 900 [Ni(CN)4]2-,

(Outer orbital Complex)
sp3d2 Octahedral 900, 900 [Cr(H2O)6]3+, [Ni(NH3)6]2+
(Outer orbital Complex)
d2sp3 Octahedral 900, 900 K4[Fe(CN)4], [Co(NH3)6]3+
(Inner orbital Complex)

-Inner Orbital complexes have strong field ligand and low spin, whereas Outer orbital complexes have
Weak field ligands and High spins.

Ex: [Cu(NH3)4]2+ dsp2 Hybridisation (Inner orbital Complex) Diamagnetic

Strong Field Ligand, Square Planar Complex

Ex: [Cr(NH3)6]3+ d2sp3 Hybridisation (Inner orbital Complex) Paramagnetic

Strong Field Ligand, Octahedral Complex

Ex: [NiCl4]2- sp3 Hybridisation (Outer orbital Complex) Paramagnetic

Weak Field Ligand, Tetrahedral Complex
Ex: [Ni(CO)4]2- sp3 Hybridisation (Inner orbital Complex) Diamagnetic
Strong Field Ligand, Tetrahedral Complex

Ex: [Ni(CN)4]2- dsp2 Hybridisation (Inner orbital Complex) Diamagnetic

Strong Field Ligand, Square Planar Complex

Ex: [Fe(CN)6]4- d2sp3 Hybridisation (Inner orbital Complex) Diamagnetic

Strong Field Ligand, Octahedral Complex
Limitations:
-This theory did not explain the weak field and strong field ligands.
-Couldn’t explain the colour formation in complexes.
-Did not give quantitative interpretation of magnetic data.
-It couldn’t explain the stability of complexes.
-----------------------------------------------------------------------------------------------------------------------------------
PREVIOUS YEAR QUESTIONS:
1) Correct order of the magnetic moment (spin only) for the following complexes is:
(JEE 2020)
A. [Pd(PPh3)2Cl2] B. [Ni(CO)4] C. [Ni(CN)4]2- D. [Ni(H2O)6]2+

a. A=B=C<D b. A<B<C<D c. A>B>C>D d. A=B>C>D

ANS: (a)

2) Complex [ML5] can exhibit trigonal bipyramidal and square pyramidal geometry.
Determine total number of 1800, 900& 1200 L-M-L bond angles
(JEE 2020)
ANS: 20

SOL:
For trigonal bipyramidal geometry
Total number of 180 L-M-L bond angles = 1 ,Total number of 90 L-M-L bond angles = 6
Total number of 120 L-M-L bond angles = 3 Total = 10 For square pyramidal geometry
Total number of 180 L-M-L bond angles = 2 Total number of 90 L-M-L bond angles = 8
Total number of 120 L-M-L bond angles = 0 Total = 10 Total for both the structures = 20

3) The complex Cr(H2O)6Cln, shows geometrical isomerism and also reacts with AgNO3
solution. Given: The spin only magnetic moment = 3.8 B.M. What is the IUPAC name of the
complex? (JEE 2020)
a. Hexaaquachromium(III) chloride b. Tetraaquadichloridochromium(III) chloride
dihydrate
c. Hexaaquachromium(IV) chloride d. Tetraaquadichloridochromium(IV) chloride
dehydrate
ANS: (b)
SOL: Spin only magnetic moment = 3.8 B.M. This implies, μ=√(n(n+2)) B.M.
(√16=4 implies that √15 should be less than four.
This means, n=3 as √15=√(3(3+2))
Cr (24) = [Ar]4s1 3d5 (g.s)
For 3 unpaired electrons, the oxidation state of Cr should be +3
Cr3+ can be attained if the complex has a structure that looks like: [Cr(H2O)4Cl2]Cl.2H2O
[Cr(H2O)4Cl2]Cl.2H2O has the IUPAC name : Tetraaquadichloridochromium(III) chloride dehydrate

4) Given following complexes: (JEE

2020)
I. Na4[Fe(CN)6] II. [Cr(H2O)6]Cl2 III. (NEt4)2[CoCl4] IV. Na3[Fe(C2O4)3] (Δ0 > P)
The correct order of spin only magnetic moment for the above complexes
a. (II)>(II)>(IV)>(I) b. (II)>(IV)>(III)>(I) c. (I)>(III)>(III)>(II) d.
(II)>(I)>(IV)>(III)
ANS: (a)

5) The degenerate orbitals of [Cr(H2O)6]3+ are:

(JEE 2019)

ANS: (1)
SOL: Octahedral complex have dxy, dyz and dzx degenerate.

6) The correct statements among I to III are

(JEE 2019)
(I) Valence bond theory cannot explain the color exhibited by transition metal complexes.
(II) Valence bond theory can predict quantitatively the magnetic properties of transition metal
complexes.
(III)Valence bond theory cannot distinguish ligands as weak and strong field ones.
(1) (II) and (III) only (2) (I), (II) and (III) (3) (I) and (II) only (4) (I) and (III) only
ANS: (4)

7) The metal d-orbitals that are directly facing the ligands in K 3[Co(CN)6] are : (JEE
2019)

ANS: (4)

8) The pair of metal ions that can give a spin only magnetic moment of 3.9 BM for the complex [M(H 2O)6]Cl2, is:
(JEE
2019)
ANS: (2)
SOL: V2+ has 3 unpaired electrons, Co2+ has 3 unpaired electrons.

9) The INCORRECT statement is :

(JEE 2019)
(1) The spin-only magnetic moments of [Fe(H2O)6]2+ and [Cr(H2O)6]2+ are nearly similar.
(2) The gemstone, ruby, has Cr3+ ions occupying the octahedral sites of beryl.
(3) The spin-only magnetic moment of [Ni(NH3)4(H2O)2]2+ is 2.83 BM.
(4) The color of [CoCl(NH3)5]2+ is violet as it absorbs the yellow light.
ANS: (2)
 SOL: Ruby is aluminium oxide (Al2O3) containing about 0.5 – 1% Cr3+ ions which are randomly
distributed in the position normally occupied by Al 3+ ions.

Crystal Field Theory:

Merits: -This theory can be used to predict the most favourable geometry of a complex.
-It accounts for the tetrahedral and square planar geometry for the same coordination number
-It is useful in interpreting magnetic properties
-Colour formation in the complexes can be easily examined.
-Crystal Filed theory explains about the ligand field strength in the form of spectrochemical series, which is
in the increasing order of ligand field strength

SPECTROCHEMICAL SERIES:

Postulates:
-This theory says that Ligands are point charges which surround the positively charged central metal
-There will be electrostatic force of attraction between the ligand and the central metal.
-As the bonding is purely ionic the complexes are crystalline in nature.
-The d –orbitals in the central metal is degenerate, but when ligands approach the central metal in a given
field the d orbitals undergo splitting
-This difference in energy of the orbitals after splitting is called (CFSE) Crystal Field Splitting Energy
denoted by Δ. Δt is for tetrahedral field and Δo is for Octahedral field
4
Δt = Δo
9
-There are only four ligands in tetrahedral complex, so ligand field is 2/3 of octahedral field.
-Hence splitting in octahedral field is more than tetrahedral field.
-All tetrahedral complexes are of high spin since CFSE is normally greater than pairing energy
Δt > P.E
-If a very strong field ligand is present then the square planar geometry favoured over tetrahedral field.
-In Octahedral field

If CFSE > P.E, then pairing of electrons occurs

If CFSE < P.E, then there is no pairing
5
Ex: In d metal complex If Δo > P.E, then t2g5, ego

If Δo < P.E, then t2g3, eg2

Ex: In d6 metal complex [MCl6]3- [M(NH3)6]3+

eg2 t2g4 eg0t2g6

 S= +2 S=0
CFSE < PE CFSE > PE
CFSE = [2x0.6 + 4x(-0.4)] Δo + 1P.E CFSE =[0x0.6 + 6x(-0.4)] Δo + 3P.E
Crystal Field splitting in Octahedral Field:

Comparison of Crystal field Splitting:

Limitations:
-This theory didn’t explain the covalent nature between the ligand and central Metal
-As the ligands are point charges, the anionic ligands should possess greater splitting of d orbital,
But they are found in the low end of spectrochemical series.
-It doesn’t account for the Pi Bond formation.

PREVIOUS YEAR QUESTIONS:

1) Which of the following statements are incorrect?
(JEE 2020)
a) Co3+ with strong field ligand forms a high magnetic moment complex.
b) For Co3+, if pairing energy (P)>Δo, then the complex formed will have t 2g4,eg2
configuration
c) For [Co(en)3]3+, λabsorbed is less than λabsorbed for [CoF6]3-
d) If Δo=18000 cm−1 for Co3+, then with same ligands for it Δt=16000 cm−1
a. A, D b. B, C c. A, B d. A, B, C, D
SOL: Co3+ has d6 electronic configuration. In the presence of strong field ligand, Δo>P. Thus the splitting
ANS: (a)

occurs as: t2g6,eg0; so the magnetic moment is zero.

This implies that the Δo of en is more than the Δo of F. Δo=hc/λabs, => Δt=4/9Δo=8000 cm−1
According to the spectrochemical series, en is a strong er ligand than F and therefore promotes pairing.

2) For [PdFClBrI]
2−
, the number of geometrical Isomers = n. Determine the spin only
magnetic moment and CFSE for [Fe(CN)6]n−6 (Ignore pairing energy).

a. 1.73 B.M.,–2Δ0 b. 2.84 B.M.,–1.6Δ0 c. 0,–1.6Δ0 d. 5.92 B.M.,–2.4Δ0

(JEE 2020)

ANS: (a)

SOL:

[Fe(CN)6]n−6 = [Fe(CN)6]3−6 = [Fe(CN)6]−3

Number of geometrical isomers (n) = 3

This implies, that Iron is in its +3 oxidation state. Fe3+(26): [Ar]3d5

CN− is a strong ligand in [Fe(CN)6]−3 and causes pairing. Hence, according to CFT, the configuration
will be t2g5 eg0.
Hence, there is only 1 unpaired electron, i.e, n=1 in √n(n+2)= √3 = 1.73 B.M
CFSE = (−0.4×nt2g+0.6×neg) Δ 0 = (−0.4×5+0.6×0) Δ 0 = -2 Δ 0

3) The complex that has highest cry splitting energy (Δ), is:
(JEE 2019)
(1) K3[Co(CN)6] (2) [Co(NH3)5(H2O)]Cl3 (3) K2[CoCl4] (4) [Co(NH3)5Cl]Cl2
Ans. (1)
SOL: Strong field CN- has high splitting energy.

4) Homoleptic octahedral complexes of a metal ion 'M 3+' with three Monodentate ligands
and L1, L2, L3 absorb wavelengths in the region of green, blue and red respectively. The
increasing order of the ligand strength is:
(JEE 2019)
(1) L2 < L1 < L3 (2) L3 < L2 < L1 (3) L3 < L1 <L2 (4) L1 < L2 < L3

Ans. (3)
Sol. Order of λabs - L3>L1>L2
1
So ΔO order will be L2 > L1 > L3 (as ΔO α |¿| )
λ ¿
So the order of ligand strength will be L2>L1>L3

5) Two complexes [Cr(H2O6)Cl3] (A) and [Cr(NH3)6]Cl3 (B) are violet and yellow coloured,
respectively. The incorrect statement regarding them is :
(JEE 2019)
(1) Δ0 value of (A) is less than that of (B).
(2) Δ0 value of (A) and (B) are calculated from the energies of violet and yellow light,
respectively
(3) Bothe absorb energies corresponding to their complementary colors.
(4) Bothe are paramagnetic with three unpaired electrons.
ANS: (2)
 6) The complex ion that will lose its crystal field stabilization energy upon oxidation of its metal to +3
state is :

(JEE
2019)

ANS: (4)
SOL:

7) Complete removal of both the axial ligands (along the z-axis) from an octahedral complex leads to
which of the following splitting patterns? (relative orbital energies not on scale).
(JEE 2019)

ANS: (2)
SOL:
The field becomes square planar and the order of energy.

8) The difference in the number of unpaired electrons of a metal ion in its high-spin and low-spin octahedral
complexes is two. The metal ion is: (JEE
2019)
(1) Fe2+ (2) Co2+ (3) Mn2+ (4) Ni2+
ANS: (2)

9) The crystal field stabilization energy (CFSE) of [Fe(H2O)6]Cl2 and K2[NiCl4], respectively, are :
(JEE 2019)
(1) –2.4o and –1.2t (2) –0.6o and –0.8t (3) –0.4o and –0.8t 4) –0.4o and –1.2t
ANS: (3)
2+ 4 2
SOL: [Fe(H2O)6] t2g eg CFSE = –0.40
2– 4 4
[NiCl4] e t2 CFSE = –0.8t

10) Three complexes, [CoCl(NH3)5]2+(l), [Co(NH3)5H2O]3+(ll) and [Co(NH3)6]3+(lll) absorb light in the
visible region. The correct order of the wavelength of light absorbed by them is :
(JEE 2019)
(1) (I) > (II) > (III) (2) (II) > (I) > (III) (3) (III) > (I) > (II) (4) (III) > (II) > (I)
ANS: (1)
SOL: In a co-ordination compound, the strong field ligand causes higher splitting of the d-orbitals.
Wavelength of the energy absorbed by the coordination compound is inversely proportional to ligand
field strength of the given coordination compound. The decreasing order of ligand field strength is NH 3
> H2O > Cl. Therefore, decreasing order of wavelength absorbed is (I) > (II) > (III).
11) The d-electron configuration of [ Ru(en)3 ] Cl2 and [ Fe(eH 2 O)6 ] Cl 2, respectively are:
(JEE 2020)
4 2 6 0 6 0 6 0
(1) t 2 g e g and t 2 g e g (2) t 2 g e g and t 2 g e g

4 2 4 2 6 0 4 2
(3) t 2 g e g and t 2 g e g (4) t 2 g e g and t 2 g e g
 Sol. 4
[ R2 u(en)3 ] Cl 2 ¿
Low spin complex High spin complex

12) The electronic spectrum of [Ti( H 2 O¿ ¿6 ¿3 +¿¿ shows a single broad peak with a maximum at 20,300 cm−1.
The crystal field stabilization energy (CFSE) of the complex ion, in kJ mol−1, is :(1 kJ mol-1 = 83.7 cm−1 )
(1) 83.7 (2) 242.5 (3) 145.5 (4) 97 (JEE
2020)
Sol . 4 1
3+ ¿3 d ¿

[Ti( H 2 O¿ ¿6 ¿3 +¿Ti ¿
in octahedral field of ligand

CFSE=−0.4 Δ 0

−0.4 × 20300
CFSE=
83.7
¿ 97 kJ mol
13) For a d4 metal ion in an octahedral field, the correct electronic configuration is: (JEE
2020)

(1) e 2g t 2g when ∆ o < P (2) t 42 e og when ∆ o < P

(3) r 32 g e 1g - when ∆ o < P (4) t 32 g e1g when ∆ o < P

Sol. 4
d4 → t 32 g e1g−∆ < P

Bonding in Metal Carbonyls:

- Carbon monoxide bonds to transition metals using "synergic π* back-bonding." The bonding has three
components, giving rise to a partial triple bond.
- A sigma bond arises from overlap of the nonbonding (or weakly anti-bonding) sp-hybridized electron pair
on carbon with a blend of d-, s-, and p-orbitals on the metal.
- A pair of π bonds arises from overlap of filled d-orbitals on the metal with a pair of π-antibonding orbitals
projecting from the carbon atom of the CO.
- The latter kind of binding requires that the metal have d-electrons, and that the metal is in a relatively low
oxidation state (<+2) which makes the back donation process favourable.
- As electrons from the metal fill the π-antibonding orbital of CO, they weaken the carbon-oxygen
bond compared with free carbon monoxide, while the metal-carbon bond is strengthened.
- Because of the multiple bond character of the M-CO linkage, the distance between the metal and carbon
atom is relatively short, often < 1.8 Å, about 0.2 Å shorter than a metal-alkyl bond.
Stability & Stability Constant of Complexes:
Formation of complexes in an aqueous solution is followed by step wise process. i.e., the complex takes
multiple steps in its formation and each step the formation of complex can be indicated with formation
constants like K1, K2, K3, ………Kn
The overall stability constant β can be expressed as the products of the stability constants of all the steps.
β = K1x K2x K3 x K4 ………Kn
 ML 4
K1xK2xK3xK4 = =β
[ M ] [ L]

Factors affecting stability:

-Ionic Size of Central Metal:
Smaller the central metal ion greater is its electrical field and more is its stability.
-Ionic Charge of Central Metal: Ferricyanide is more stable than Ferrocyanide.
-Electronegativity: More the electronegativity of a metal more is its stability.
-Metal which has more incomplete orbitals can accept more shared pair of electrons to increase the
stability.
-Metal Carbonyls are more stable due to the presence of Back bonding.
- Stronger the ligand field strength more is the stability of complex.
- The closed ring complexes formed by polydenatate ligands are called Chelates. Chelation leads to
stability.
Applications of Complexes:
Metallurgy- Extraction of Gold [Au(CN)2]- and Silver [Ag(CN)2]- and in refining of metals like Ni
[NI(CO)4]
Medicine- Cis Platin is used as cure for Cancer and inhibits the growth of tumours in the body
And chelate therapy which is the removal of toxic proportion of
Industry- As a catalyst in conversion of Vegetable oil to Ghee [(Ph3P)3 Rh Cl] (Wilkinson’s catalyst)
Biological Significance-Blood consist of Haemoglobin which is a complex of Iron and the green pigment
present in plants is a complex of Mg.
Photography- SilverThiosulphate complexes are formed in black & white photography
Qualitative and Quantitative Analysis- K4[Fe(CN)6] is used in the identification of metals and
Sodiumnitro Prusside is used in identification of Sulphur and Thiocyanide complex is used in
estimation of N & S
EDTA is used in the removal of Permanent hardness of water
Applications of Organometallic Compounds
(i) Tetra ethyl lead (TEL) is used as antiknock compound in gasoline.
(ii) Wilkinson's catalyst [Rh(PPh3)3Cl] is use as homogeneous catalyst in the hydrogenation of alkenes.
(iii) The extraction and purification of nickel is based on the formation of organometallic compound
Ni(CO)4.
The formation of Ni(CO)4 at 50-80ºC and its decomposition at 150-180ºC is used in the extraction of
nickel by MONDS PROCESS.
 (iv) Zeigler Natta catalyst (trialkyl aluminium + titanium tetrachloride) acts as a heterogeneous catalyst in
the polymerisation of ethylene in to polyethylene polymer.
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PREVIOUS YEAR QUESTIONS:
1) The compound that inhibits the growth of tumour is: (JEE
2019)

ANS: (1)
2) Mn2(CO)10 is an organometallic compound due to the presence of:
(JEE 2019)
(1) Mn – Mn bond (2) Mn – C bond (3) Mn – O bond (4) C – O
bond
ANS: (2)
SOL:

3) The compound used in the treatment of lead poisoning is:

(JEE 2019)
(1) EDTA (2) desferrioxime B (3) Cis-platin (4) D-penicillamine
ANS: (1)
4) The number of bridging CO ligand (s) and Co-Co bond (s) in CO 2(CO)g, respectively are:
(JEE 2019)
(1) 0 and 2 (2) 2 and 0 (3) 4 and 0 (4) 2 and 1
ANS: (4)
SOL:

5) Match the metals (Column I) with the coordination compound(s) / enzyme(s) (Column II) (JEE
2019)

ANS: (2)
6) The electrolytes usually used in the electroplating of gold and silver, respectively, are: (JEE
2019)

ANS: (4)
7) The equation which is balanced and represents the correct product(s) is: (JEE
2014)

ANS: (4)
SOL: Equation – 1 is not balanced w.r.t. charge.
Equation – 2 gives K3 [Cu(CN)4] as product.
Equation – 3 reaction is unfavourable in the forward direction (K2O is unstable, while Li2O is stable).
Equation – 4 is correct & balanced.

8) In a complexometric titration of metal ion with ligand

M (Metal ion) + L (Ligand) C (Complex) end point is estimated spectrophotometrically (through light
absorption). If 'M' and 'C' do not absorb light and only 'L' absorbs, then the titration plot between
absorbed light (A) versus volume of ligand 'L' (V) would look like: (JEE
2018)

ANS: (1)
SOL: Initially ligand consumed by metal due to formation of complex. So absorbed light (A) remain constant,
after complex formation is completed, extra volume of ligand solution increases ligand concentration
and also increases absorbed light.

9) In Wilkinson's catalyst, the hybridization of central metal ion and its shape are respectively: (JEE
2018)
(1) sp3d, trigonal bipyramidal (2) d2sp3, octahedral (3) dsp2, square planar (4) sp3, tetrahedral
ANS: (3)