Real life importance of Coordination Compounds

The chemistry of coordination compounds is an important and

challenging area of modern inorganic chemistry. Variety of metallurgical
processes, industrial catalysts and analytical reagents involve the use of
coordination compounds. Coordination compounds also find many
applications in electroplating, textile dyeing and medicinal chemistry.

College related importance of Coordination Compounds

Coordination compounds are employed in hydrometallurgical processes for

the extraction of metals such as nickel, cobalt, and copper from their ores
and in crucial catalytic processes to bring about polymerization of organic
compounds such as polyethylene and polypropylene.
 JEE Main Exam

Coordination Compounds
Percentage Weightage (2019-24)

Inorganic Chemistry 17.66 %

 JEE Advanced Exam
Inorganic Chemistry: Relative Weightage (2019-24)

Coordination Compounds
21.40 %
Pre-requisite chapters

Periodic Table

Chemical Bonding and Molecular Structures

The d- and f-Block Elements

 Salt

Neutralisation product of acid and base is known as salt.

HCl (aq.) + NaOH (aq.) ⎯⎯→ NaCl (aq.) + H2O (aq.)

Salt
Type of salts

Simple salts
Type of Salts Double salts

Addition salts

Complex salts

Note

Complex salt are also known as Coordination compounds

Complex Salts

The addition compounds in which some of the constituent ions or

molecules lose their identity, and when dissolved in water they do
not break up completely into individual ions are called complex salt

Individual test of all constituent ions can not be obtained from its
aqueous solution.
 Complex Salts

EXAMPLE

Crystallization
4KCN (aq.) + Fe(CN)2 (aq.) 4KCN.Fe(CN)2

H2O
K4[Fe(CN)6] 4K+ + [Fe(CN)6]4–
(Potassium ferro cyanide)
 Terminology used in complex (salts)

Central metal atom/ion

Ligand

Number of ligands

K4 [Fe (CN) 6 ]

counter ion coordination sphere

Number of ligands = 6
Coordination number = 6
LIGAND

A ligand is an ion or molecule that binds to a central metal atom to

form a complex (alternatively known as a coordination entity).
 Types of
Complexes

On the basis of On the Basis of nature On the Basis of

stability of Complex ion Type of Ligands

Perfect Cationic Homoleptic

complexes complexes complexes

Anionic
Imperfect Heteroleptic
complexes
complexes complexes
Neutral
complexes
 Example

Identify homoleptic and heteroleptic complexes

K4[Fe(CN)6] ⎯⎯→ homoleptic complex

[Co(en)2(NH3)2]Cl2 ⎯⎯→ heteroleptic complex

[Fe(CO)5] ⎯⎯→ homoleptic complex

Na[Cr(ox)2(H2O)2] ⎯⎯→ heteroleptic complex

 Example

Identify cationic, anionic and neutral complexes

K4[Fe(CN)6] ⎯⎯→ Anionic complex

[Cr(H2O)6]Cl3 ⎯⎯→ Cationic complex

[Fe(CO)5] ⎯⎯→ Neutral complex

Na[Cr(ox)2(H2O)2] ⎯⎯→ Anionic complex

 Type of the Ligands
on the basis of

Nature of
Charge Denticity Bonding

Cationic Monodentate Classical

Anionic Polydentate Non-Classical

Neutral
 Classification of ligands ON THE BASIS OF CHARGE

1. Cationic (positive) ligands

Ligands which can carry positive charge and their name end with ‘ium’.

EXAMPLE

Cationic Ligand Formula Name of Cationic Ligand

NO+ (N ≡ O) nitrosonium /nitrosylium

N2H5+ (NH2—NH3) hydrazinium

NO2+ nitronium

O2+ oxygenium
 Classification of ligands ON THE BASIS OF CHARGE

2. Anionic (Negative) ligands

Ligands which can carry negative charge and their name end with ‘o/ido’.

EXAMPLE

Anionic Ligand Formula Name of Anionic Ligand

F- fluoro/fluorido
O2- oxo/oxido
O22- peroxo/peroxido
O2- superoxo/superoxido
 Classification of ligands ON THE BASIS OF CHARGE

3. Neutral ligands

Ligands which can carry no charge and no suffix will be added in

their name. Generally, we use common name

Neutral Ligand Formula Name of Neutral Ligand

O2 Dioxygen
N2 Dinitrogen
C5H5N Pyridine (py)
N2H4 Hydrazine
 Classification of ligands On the basis of denticity

1. Monodentate ligands

Ligands which can share one pair of electron to the central atom
are called monodentate ligands.
 Classification of ligands On the basis of denticity

EXAMPLE

Ligand Name of Anionic Cationic Neutral

Monodentate
Formula Ligand Ligand Ligand Ligand
NH2– amido
NH2- imido
N3– nitrido
N 3– azido
fluoro /
F– fluorido
chloro/
Cl–
chlorido
 Ligand Anionic Cationic Neutral
Name of Ligand Monodentate
Formula Ligand Ligand Ligand
Br– bromo/bromido
I– iodo/iodido
H- hydrido
O2- oxo/oxido
O22- peroxo/peroxido
superoxo/
O2-
superoxido
CH3COO acetato
CO32– carbonato
SO42– sulphato
OH- hydroxo/hydroxide

S2O32– thiosulphato
 Ligand Anionic Cationic Neutral
Name of Ligand Monodentate
Formula Ligand Ligand Ligand
SO32– sulphito
HCOO– formato
–NO2– nitrito – N
–ONO nitrito – O
-SCN– thiocyanato– S
-NCS– thiocyanato – N
CN- cyano/cyanido
-CNO– cyanato
-ClO3– chlorato
H2O aqua
CO carbonyl
ammine /
NH3 ammonia
 Ligand Anionic Cationic Neutral
Name of Ligand Monodentate
Formula Ligand Ligand Ligand
NO nitrosyl
CS thiocarbonyl
NS thionitrosyl
PH3 phosphine
(C2H5)3P triethylphosphine
NHEt2 diethylamine
PF3 trifluorophosphine
(C6H5)3P triphenylphosphine
CH3NH2 Methylamine
CH3OCH3 Dimethyl ether
C2H5OC2H5 Diethyl ether
CH3NC methylisocyanide
Structure of some monodentate ligands

EXAMPLE

••
P
N N

••

••
N
••
pyrazine
Pyridine (py)
(Neutral)
(Neutral) triphenyl phosphine (PPh3)
(Neutral)
 Classification of ligand On the basis of denticity

2. Polydentate ligands

Ligands which can share more than one pair of electrons with
central atom.

Except monodentate ligands all are polydentate ligands.

 (A) Bidentate Ligands

(B) Tridentate Ligands

Polydentate (C) Tetradentate Ligands

ligands

(D) Pentadentate Ligands

(E) Hexadentate Ligands

(A) Bidentate Ligands

*
CH3 — CH — CH2
| |
NH2 NH2
•• ••
pn : Propylene diamine or Propane - 1, 2 - diamino

CH2 — CH2 — CH2

| |
NH2 NH2
•• ••
CH3 tn : Trimethyl diamine or Propane - 1, 3 - diamino
|
CH3 — C — CH2
| |
NH2 NH2
•• ••
isobutylenediamine (i - bn)
EXAMPLE (Acetylacetone)
H3C — C — CH2 — C — CH3
|| ||
O O
Keto form

H3C — C — CH = C — CH3
|| |
O OH
Enol form

– H+

H3C — C — CH = C — CH3
|| |
O O–
•• ••

acac– : Acetylacetonato
 (A) Bidentate Ligands

Symmetrical Unsymmetrical
bidentate ligands bidentate ligands

Are those bidentate Are those bidentate

ligands having similar ligands having not
donor sites. similar donor sites.
 Symmetrical Unsymmetrical
bidentate ligands bidentate ligands

CH3—C—CH=C—CH3

O O
O

H2N—CH2—C
M O–
acac (acetyl acetonato)
M
CH2—NH2
M gly (glycinato)

CH2—NH2

en (ethylene diamine)
(B) Tridentate ligands

CH2—CH2—NH—CH2—CH2

H2N NH2

M
dien : Diethylenetriamine

–OOC — CH2 — NH — CH2 — COO–

••

M
imda2– : Imino diacetato
(C) Tetradentate ligands

CH2 — CH2 —NH — CH2 — CH2

••

HN NH2

••
••

H2C M

H2C
•• trien : triethylenetetraamine
NH2

••
–OOC CH2 N CH2 COO–

CH2
NTA3– : Nitrilo triacetato
COO–
(D) Pentadentate ligands

–OOC—CH
2
CH2—COO–
•• ••
N—CH2—CH2—N
H CH2—COO–

EDTA3– : ethylenediaminetriacetato

•• ••
CH2—CH2—NH—CH2—CH2—NH2
••
NH •• ••
CH2—CH2—NH—CH2—CH2—NH2

tetraethylenepentaamine (tetraen)
(E) Hexadentate ligands

–OOC—CH
2
CH2—COO–
•• ••
N—CH2—CH2—N
–OOC—CH
2
CH2—COO–

EDTA4– : ethylenediaminetetraacetato
 Example

EDTA4⊝ is ethylenediamminetetraacetate ion. The total number of

N—Co—O bond angles in [Co(EDTA)]1⊝ complex ion is

Solution

Ans : (8)
Chelating ligands

For every polydentate ligand a ring like structure is formed when

bonded with central metal atom/ion. This is called chelate ring and
corresponding ligand is called chelating ligand.

All the polydentate ligands are chelating ligands.

CH2—NH2
5 membered
M
chelate ring
CH2—NH2

en (ethylene diammine)
Ambidentate ligands

Monodentate ligand which have more than one type of donor site but
at a time only one type of donor site can share their electron pair
with central atom.

Ambidentate ligands can produce different types of metal ligand

linkage.

C N

••
 
(a) M C N (b) C N M

••

••
cyanido-C cyanido-N

(C-atom coordinated to metal) (N-atom coordinated to metal)

EXAMPLE

[Fe(CN)6]4– [Fe(NC)6]4–

O—C N

••
– –
(a) M O—C N (b) O—C N M

••

••
cyanato-O cyanato–N
(O-atom coordinated to metal) (N-atom coordinated to metal)


S
••
••
C N

– –
(a) M S C N (b) S C N M
••

••
•• ••

thiocyanato-S thiocyanato-N
(S-atom coordinated to metal) (N-atom coordinated to metal)
 O
N

••
O–

O
(a) M N (b) M Oഥ — N = O

••
O–

••
••

Nitrito-N Nitrito-O

(N-atom coordinated to metal) (O-atom coordinated to metal)

Flexidentate ligands

Ligands which show flexibility in denticity are called flexidentate

ligand.

EXAMPLE

•• ••
CO2–
3 , SO2–
4 , SO2–
3 , NO–3 , N2, O2, NH2 — NH2, PO43- , CH3—COO etc.
Flexidentate ligands

O
NH3
NH3 S O


  NH3 O
NH3 O O Co3+ S
Co3+ O NH3 
O O
NH3
NH3 NH3
NH3

[Co(NH3)5(SO4)]Cl [Co(NH3)4(SO4)]Cl
Flexidentate ligands

When these ligands behave as monodentate ligands, the complexes so

formed are really stable. But when these ligands behave as bidentate
ligands, they form chelates containing three or four membered rings
including metal ion or atom.

In general, the chelates having three or four membered ring are

unstable because of the steric strain.
Bridging ligands

The ligands in which one or two different donor atoms have atleast
two pairs of electrons and share these electron pairs with two metal
ions or atoms (one pair with one atom or ion) simultaneously are
called bridging ligands.

The interaction of bridging ligands with metal ions or atoms can be

represented as M  :L: → M.
 Bridging ligands

EXAMPLE

•• •• •• ••
H2O:, OH–, :NH2—, F—, Cl—, Br— , I— , O2– , :SCN–:, :CO:, :CN:–, NH2 , —
•• ••
••
NH2, NO2–, O22–, O22–, SO32-, SO42–, ClO3–, pyrazine, :N N: etc.
Organic ligands

No suffix will be added in the name of organic ligand.

EXAMPLE

 
CH3 → Methyl C2H5 → Phenyl


C6H5 C2H4 → H2C == CH2
or → Phenyl
 η2 – ethene
Ph
Hapticity

Hapticity is the coordination of a ligand to a metal atom/ion via

contiguous series of atoms

Represented by Greek letter ‘𝜂’.

EXAMPLE

C3H5


(a) σ — C3H5 (b) 𝜋 — C3H5

CH CH
– –
CH2 CH2 CH2 CH2
••

••

Allyl η3 – Allyl
 EXAMPLE


C4H4 C5H5

η4 – cyclobutadiene 

(a) 𝜎 – C5H5– (b) π – C5H5–

Cyclopentadienyl η5 - cyclopentadienyl
IUPAC NOMENCLATURE
 IUPAC Nomenclature

Rules

1 The cation is named first followed by the anion and the cation is
separated by a space from the anion. No space is used within the
name of the complex ion. If a coordination compound is ionic

Contains either a complex cation,

Complex anion or both .
Rules

2 If a coordination compound is neutral, the name of compound is

written as one word (i.e. the name of neutral complex compound is
given without space).

3 In the name of a complex ion or neutral complex ligands are

arranged according to their alphabetical order first, followed by
central atom/ion name.

4 Oxidation state of central atom/ion is written in small bracket

with the help of Roman numeral. (Immediately after the name of
central atom/ion)
 Rules

5 If central atom/ion is present in an anionic complex, then “ate”

suffix will be added in its name. for a complex cation or neutral
complex, the usual name of the metal is used.

Metal Name Metal Name

B Borate Mn Manganate
Al Aluminate Sc Scandate
Ca Calcate Co Cobaltate
Cr Chromate Ni Nickelate
IUPAC Nomenclature

Metal Name Metal Name

Cd Cadmate Pt Platinate
Zn Zincate Mercurate /
Hg
Hydragurate
Mo Molybdate
Rh Rhodate Fe (iron) Ferrate

Pd Palladate Cu (copper) Cuprate

Os Osmate Ag (silver) Argentate

Ti Titanate Au (gold) Aurate

V Vanadate Sn (tin) stannate

Ir Iridate Pb (lead) plumbate

 Rules

6 If the complex ion or neutral complex contains more than one

ligand of a particular kind, the prefixes di, tri, tetra, penta, hexa
and so forth are used. (Not considered for alphabetical order)

7 If word like di, tri, tetra, penta, hexa is already used in the name
of ligand then prefix will be used as bis, tris, tetrakis, pentakis,
hexakis to specify the number of ligands.

(The prefixes bis, tris, tetrakis and so forth are also used for
complex ligands.)
 Note

The vowel ending the numeral prefix of the ligands will not be ignored
while writing the name.

EXAMPLE

Four NH3 ligands ⎯→ tetraammine

Three oxide ligands ⎯→ trioxide

Exception

Mono + oxide ⎯→ monoxide

 EXAMPLE

[Ni(dmg)2]

Bis(dimethylglyoximato)nickel(II)
(a) Non- ionic or Neutral Complexes

Metal Name

[Co(NH3)3Cl3] triamminetrichlorocobalt(III)

triamminetrinitrocobalt(III)
[Co(NH3)3 (NO2)3] Or
triamminetrinitrito-N cobalt(III)

Ni(CO)4 tetracarbonylnickel(0)

Fe(C5H5)2 bis(cyclopentadienyl)iron(II)

[Cu(CH3NH2)2Cl2] dichlorobis(methylamine)copper(II)
(b) Complexes Containing Complex Cations

Metal Name

[Co(NH3)6]Cl3 hexaamminecobalt(III) chloride

[Co(NH3)5 Cl]Cl2 pentaamminechlorocobalt(III) chloride

[Co(NH3)4 (H2O)2]Cl3 tetraamminediaquacobalt(III) chloride

[Co(en)3]Cl3 tris(ethylenediamine)cobalt(III) chloride

tetraamminechloronitrocobalt(III) chloride
Or
[Co(NH3)4 (NO2)Cl]Cl
tetraamminechloridonitrito-N cobalt(III)
chloride
(c) Coordination Compounds Containing Complex Anions

Metal Name

sodium aquadibromoethylenediamine
Na2[Ni(en)(SO4)Br2H2O]
sulphatonickelate(II)

K2[Co(N3)4] potassium tetraazidocobaltate(II)

Fe4[Fe(CN)6]3 iron hexacyanoferrate(II)

sodium amminebromochloronitrito-N
Na[PtBrCl(NO2)(NH3)]
platinate(II)
potassium ethylenediaminetetraacetato
K[Co(EDTA)]
cobaltate(III)
(d) Naming of Coordination compound having Cation and Anion both as
Complex Ions

Metal Name

[Pt(NH3)4][PtCl4] tetraammineplatinum(II) tetrachloroplatinate(II)

[Pt(NH3)4Cl2][PtCl4] tetraamminedichloroplatinum(IV) tetrachloroplatinate(II)

[Co(en)3] [Cr(CN)6] tris(ethylenediamine)cobalt(III) hexacyanochromate(III)

WERNER'S THEORY OF
COORDINATION
COMPOUNDS
 Werner’s Theory of coordination compounds

Alfred Werner prepared and characterised a large number of

coordination compounds and studied their physical and chemical
behaviour by simple experimental techniques.

Alfred Werner
 Werner’s Theory of coordination compounds

According to Werner’s theory, metal atom/ion forming coordination

compounds exhibits two types of valencies :

Primary valency

Corresponds to the oxidation

number of metal
Secondary valency

Corresponds to the coordination

number of metal

All the metal atom/ion have tendency to satisfy both their valencies.
Difference between primary and secondary valency

Primary valency Secondary valency

It is satisfied by negative It is satisfied by negative

ions. ions or neutral molecules or
both.

Normally ionisable Non − ionisable

Non-directional Directional

Negative ions satisfying the The secondary valency are

primary valency do not give directed in space to give a
any geometry to coordination definite geometry to the
compound complex

Denoted by dotted lines Denoted by solid lines

 Mn+

Dotted line indicates primary valency

Mn+

Solid line indicates secondary valency

Mn+

It indicates primary and secondary valency Both

 Werner studied the structure and properties of the following four
complexes of Co(III) chloride with ammonia which have different
colours.

Compounds No. of No. of Ions

Colour Charge on
Old Formula New Formula Complex Ion Cation Anion Total
CoCl3.6NH3 [Co(NH3)6]Cl3 Yellow +3 1 3 4

CoCl3.5NH3 [Co(NH3)5Cl]Cl2 Purple +2 1 2 3

trans-
CoCl3.4NH3 Green +1 1 1 2
[Co(NH3)4Cl2]Cl
cis-
CoCl3.4NH3 Violet +1 1 1 2
[Co(NH3)4Cl2]Cl
Blue
CoCl3.3NH3 [Co(NH3)3Cl3] green — — — —
 CoCl3.6NH3
Cl
Excess AgNO3
H3N NH3
CoCl3.6NH3 ⎯⎯⎯⎯⎯⎯→ 3AgCl

H3N Co NH3

[Co(NH3)6]Cl3 ⎯→ [Co(NH3)6]3+ + 3Cl– Cl Cl

H3N NH3

3Ag+ + 3Cl– ⎯→ 3AgCl(s)

All the three chlorides ion satisfy only primary valency and the six
ammonia molecules satisfy only the secondary valency
 CoCl3.5NH3

Excess AgNO
CoCl3.5NH3 ⎯⎯⎯⎯⎯⎯→
3
2AgCl Cl
H3N NH3

H3N Co Cl
[Co(NH3)5Cl]Cl2 ⎯→ [Co(NH3)5 Cl]2+ + 2Cl–

H3N NH3
Cl
2Ag+ + 2Cl– ⎯→ 2AgCl(s)

One chloride ion satisfy a primary as well as secondary valency.

 CoCl3.4NH3

CoCl3.4NH3 ⎯⎯⎯⎯⎯→
3 Excess AgNO
AgCl Cl
H3N NH3

[Co(NH3)4Cl2]Cl ⎯→ [Co(NH3)4Cl2]+ + Cl– Co Cl

H3N NH3
Ag+ + Cl– ⎯→ AgCl(s)
Cl

Two chloride ions satisfy a primary as well as secondary valency.

CoCl3.3NH3

Cl
Excess AgNO3
CoCl3.3NH3 ⎯⎯⎯⎯⎯→ × H3N NH3

Three chloride ions satisfy a primary Co

as well as secondary valency.

H3N Cl
This compound does not give any Cl
precipitate with AgNO3 solution
 How
many Cl– Total Total no. of Percentage
Complex act as a no. of moles of of
Compound P.V. & ions in AgCl when ionisable
S.V. aq. AgNO3 used chlorine
both

PtCl4. 6H2O [Pt(H2O)6]Cl4 0 5 4 mole 100%

PtCl4. 6H2O [Pt(H2O)5Cl]Cl3 1 4 3 mole 75%

PtCl4. 6H2O [Pt(H2O)4Cl2]Cl2 2 3 2 mole 50%

PtCl4. 6H2O [Pt(H2O)3Cl3]Cl 3 2 1 mole 25%

 Example

In the compound CoCl3.5NH3

(A) All the Cl show Primary valency only
(B) Two Cl show Primary valency and one Cl show Secondary valency only
(C) Two Cl show Primary valency and one Cl show Primary valency as well as
Secondary valency
(D) All the Cl show Secondary valency

Solution

Ans : C
 Example
Assign secondary valences to metals in the following compounds:

Moles of AgCl precipitated per mole

Formula
of the compounds with excess AgNO3

(i) PdCl2. 4NH3 2

(ii) NiCl2. 6H2O 2
(iii) PtCl4. 2HCl 0
(iv) CoCl3. 4NH3 1
(v) PtCl2. 2NH3 0

Ans (i) Secondary 4 (ii) Secondary 6

Solution
(iii) Secondary 6 (iv) Secondary 6
(v) Secondary 4
 Example

On treatment of 100 mL of 0.1 M solution of CoCl3.6H2O with excess

AgNO3; 1.2 × 1022 ions are precipitated. The complex is :-
(1) [Co(H2O)4Cl2]Cl.2H2O (2) [Co(H2O)3Cl3].3H2O
(3) [Co(H2O)6]Cl3 (4) [Co(H2O)5Cl]Cl2.H2O

Solution [JEE (MAIN) 2017 Offline]

Ans : (1)
 Example

The oxidation states of Cr in [Cr(H2O)6] Cl3,[Cr(C6H6)2], and

K2[Cr(CN)2(O)2(O2)(NH3)] respectively are :
(1) +3, +2, and +4 (2) +3, 0, and +6
(3) +3, 0, and +4 (4) +3, +4, and +6
[JEE (MAIN) 2018 Offline]
Solution

Ans : (2)
 Electrical conductance or Molar conductance

Electrical conductance or molar conductance of a substance depends

upon the number of charges on the particles furnished by the
substance in aqueous solution.

Electrical Conductance ∝ Number of ions

If number of ions are same, then

Electrical conductance ∝ Charge on ions

EXAMPLE

[Co(NH3)6]Cl3 > [Co(NH3)5Cl]Cl2 > [Co(NH3)4Cl2]Cl > [Co(NH3)3Cl3]

 Example

Which of the following compounds have highest electrical conductance ?

(A) CoCl3.5NH3 (B) CoCl3.4NH3
(C) CoCl3.6NH3 (D) CoCl3.3NH3

Solution

Ans : C
Limitations of werner’s theory

Werner’s theory is unable to explain magnetic properties, relative

stability , colouration, geometry of coordination compound.
SIDGWICK THEORY OF
EFFECTIVE ATOMIC
NUMBER (EAN)
 Sidgwick theory of effective atomic number (ean)

EAN of Atomic number of central atom – (O.N. of central atom)

central atom = + (total number of electrons obtained from various ligands)
 EAN Rule
No. of No. of
Atomic
Complex Ion Number Oxidation Electrons Electrons EAN
State of on Metal Donated
of the
the Metal Cation / by the
Metal
Atom Ligands

[Co(NH3)6]3+ 27 +3 24 2 × 6 = 12 24 + 12 = 36(Kr)

[Fe(CN)6]4– 26 +2 24 2 × 6 = 12 24 + 12 = 36(Kr)

[Cu(CN)4]3– 29 +1 28 2×4=8 28 + 8 = 36(Kr)

 EAN Rule
No. of No. of
Complex Ion Atomic Oxidation EAN
Electrons on Electrons
Number of State of
Metal Cation Donated by
the Metal the Metal
/Atom the Ligands

[Cr(CN)6]3– 24 +3 21 2 × 6 = 12 21 + 12 = 33

[NiCl4]2- 28 +2 26 2×4=8 26 + 8 = 34

[Ni(CN)4]2- 28 +2 26 2×4=8 26 + 8 = 34

[PdCl4]2– 46 +2 44 2×4=8 44 + 8 = 52
This rule is still well applicable for carbonyl compounds (Metal carbonyls).

EAN Rule
No. of No. of
Atomic
Complex Ion Number Oxidation Electrons Electrons EAN
State of on Metal Donated
of the
the Metal Cation / by the
Metal
Atom Ligands
Fe(CO)5 26 0 26 2 × 5 = 10 26 + 10 = 36(Kr)

Cr(CO)6 24 0 24 2 × 6 = 12 24 + 12 = 36(Kr)

Ni(CO)4 28 0 28 2×4=8 28 + 8 = 36(Kr)

Exception V(CO)6

EAN = 23 – 0 + 6 × 2 = 35 (does not follow EAN yet exists)

Calculation of E.A.N in -bonded complexes

All −electrons should be counted in calculation of EAN in −bonded

complexes

EXAMPLE

[Fe(𝜂 5 –C5H5)2]

EAN = 26 – 2 + 6 × 2 = 36 (follow EAN)

EXAMPLE

[Cr(𝜂 6 –C6H6)2]

EAN = 24 – 0 + 6 × 2 = 36 (follow EAN)

Note

Nitrosyl group (NO) is a 3 electron donor.

NO+ NO
(2e- donor) (3e- donor)

Brown ring complex

[Cr(NO)4]
[Fe(H2O)5(NO)]SO4
EAN = 24 – 0 + 4 × 3 = 36
EAN = 26 – 1 + 5 × 2 + 1 × 2 = 37

Sodium nitroprusside
[Fe(CO)2(NO)2]
Na2[Fe(CN)5(NO)]
EAN = 26 – 0 + 2 × 2 + 3 × 2 = 36
EAN = 26 – 2 + 5 × 2 + 1 × 2 = 36
 EXAMPLE

Mn(CO)5 (monomeric form)

EAN = 25 – 0 + 10 = 35
(does not follow EAN rule and hence monomer does not exist)

Mn(CO)5

reduced in
presence of Dimerised
reducing agent

[Mn(CO)5]– [Mn2(CO)10]

EAN = 25 – (-1) + 10 = 36 EAN = 25 – 0 + 2 × 5 + 1 = 36

 EXAMPLE

Co(CO)4 (monomeric form)

EAN = 27 – 0 + 4 × 2 = 35
(does not follow EAN rule and hence monomer does not exist)

Co(CO)4

reduced in
presence of Dimerised
reducing agent

[Co(CO)4]– [Co2(CO)8]

EAN = 27 – (-1) + 4 × 2 = 36 EAN = 27 – 0 + 3 × 2 + 2 + 1 = 36

STRUCTURAL
ISOMERISM
Isomerism

Isomers are two or more compounds that have the same molecular
formula but a different arrangement of atoms, and the phenomenon
of existence of isomers is called isomerism.

Since their atoms are arranged differently, therefore, isomers are

different compounds with different reactivity and/or of different
physical properties (such as colour, melting and boiling points, and
solubility).
 Structural Isomerism Stereoisomerism

Ionisation isomerism Geometrical isomerism

Hydrate or solvate isomerism

Optical isomerism
Linkage isomerism

Coordination isomerism

Coordination - position isomerism

Ligand isomerism

Polymerisation isomerism
Structural Isomerism

Compounds which are having same molecular formula but different

structure (connectivity of ligand is different) are known as
structural isomers and this phenomenon is known as structural
isomerism.
Ionisation isomerism

Coordination compounds having same molecular formula but produce

different ions in aqueous solution they are called ionisation isomer of
each other.

This arise when a ligand can be exchanged with counter ions.

They can be differentiated by ppt. method/conductivity measurement.

 EXAMPLE

[Co(NH3)5 SO4]Br [Co(NH3)5Br] SO4

Ions in water : Ions in water :

[Co(NH3)5 SO4] + [Co(NH3)5Br] 2+

Br – SO4 2–

Excess AgNO3 : Excess BaCl2 :

AgBr (↓) (Yellow ppt.) BaSO4 (↓) (White ppt.)

 EXAMPLE

(i) [Co(NH3)5 Cl]SO4 and [Co(NH3)5(SO4)]Cl

Ionisation Isomer

(ii) [Co(NH3)5 (NO3)]SO4 and [Co(NH3)5(SO4)]NO3

Ionisation Isomer

(iii) [Pt(NH3)4 Cl2]Br2 and [Pt(NH3)4 Br2]Cl2

Ionisation Isomer
Hydrate or solvate isomerism

When water molecules are exchanged between coordination sphere

and ionisation sphere, the resulting isomers are called hydrate
isomer.

They can be differentiated by quantitative estimation of ppt,

conducting method or by using suitable dehydrating agent (conc.
H2SO4).
Hydrate or solvate isomerism

EXAMPLE

CoCl3.6H2O

[Co(H2O)6]Cl3

[Co(H2O)5Cl]Cl2.H2O
Hydrate isomers
[Co(H2O)4Cl2]Cl.2H2O

[Co(H2O)3Cl3].3H2O
Linkage isomerism

This isomerism arises when complex have atleast one ambidentate

ligand.

Such isomers have different metal ligand linkage and they are
differentiated by their colour or  absorbed for d–d transition.
Some examples of Ambidentate ligands are —


C N

••
 
(a) M C N (b) C N M

••

••
cyanido-C cyanido-N

(C-atom coordinated to metal) (N-atom coordinated to metal)


O—C N

••
– –
(a) M O—C N (b) O—C N M

••

••
cyanato-O cyanato–N
(O-atom coordinated to metal) (N-atom coordinated to metal)
 
S C N

••
••

– –
(a) M S C N (b) S C N M

••

••
•• ••

thiocyanato-S thiocyanato-N
(S-atom coordinated to metal) (N-atom coordinated to metal)

•• N
O–
O
(a) M N (b) M Oഥ — N = O

••
O–

••
••

Nitrito-O Nitrito-N
(N-atom coordinated to metal) (O-atom coordinated to metal)
 EXAMPLE

1. [Pd (PPh3)2 (SCN)2] and [Pd (PPh3)2 (NCS)2]

Linkage Isomer

2. [Co (en)2 (NO2)2]+ and [Co (en)2 (ONO)2]+

Linkage Isomer
 EXAMPLE

[Cr (H2O)4 (SCN) (NO2)]Br

[Cr (H2O)4 (NCS) (NO2)]Br

Linkage isomers
[Cr (H2O)4 (NCS) (ONO)]Br

[Cr (H2O)4 (SCN) (ONO)]Br

Coordination isomerism

This isomerism arises when both cationic and anionic parts of

compound are complex part.

Such isomers are formed by exchanging either central atoms or

ligands.
 EXAMPLE

[Co(NH3)6] [Cr(CN)6]

[Co(NH3)5CN] [Cr(CN)5 (NH3)]

[Co(NH3)4(CN)2] [Cr(CN)4(NH3)2]
Coordination isomers
[Co(NH3)2(CN)4] [Cr(CN)2(NH3)4]

[Co(NH3)(CN)5] [Cr(CN)(NH3)5]

[Co(CN)6] [Cr(NH3)6]

Note

[Co (NH3)3 (CN)3] [Cr (CN)3 (NH3)3] ⎯→ (Does not exist)

Coordination Position Isomerism

This type of isomerism arises due to exchange of terminal ligands

(non-bridging ligands) between two metal cations.

4+
NH2
(H2O)3 (NH3) Co Co (NH3)3 (H2O)
OH

and
4+
NH2
(H2O)4 Co Co (NH3)4
OH
EXAMPLE

NH2
[(H3N)4 Co Co (NH3)2 Cl2]2+
O2

and

NH2
[Cl (H3N)3 Co Co (NH3)3 Cl]2+
O2
 EXAMPLE

OH
[(H3N)4 Co Co (NH3)2 Cl2]2+
OH

and

OH
[Cl (H3N)3 Co Co (NH3)3 Cl]2+
OH
Ligand Isomerism

This type of isomerism arises when ligand itself show isomerism.

Or

If a ligand itself exists in two or more isomeric forms, then the

complexes containing such ligands also exist in isomeric forms.

EXAMPLE

pn : Propylene diamine tn : Trimethylene diamine

CH3 — CH — CH2 CH2 — CH2 — CH2

| | | |
NH2 NH2 NH2 NH2
•• •• •• ••
 Polymerisation Isomerism

It is not true isomerism because it occurs between compounds

having the same empirical formula but different molecular mass.

Number of
Complex compound Ratio
Co3+ NH3 NO2 –

[Co(NH3)3(NO2)3] 1 3 3

Polymerisation [Co(NH3)6][Co(NO2)6] 2 6 6 1:3:3

isomer
[Co(NH3)4(NO2)2][Co(NH3)2(NO2)4] 2 6 6
 EXAMPLE

Number of
Complex compound Ratio
Pt2+ NH3 Cl–

[Pt(NH3)2Cl2] 1 2 2

[Pt(NH3)4][PtCl4] 2 4 4
Polymerisation 1:2:2
isomer
[Pt(NH3)4][Pt(NH3)Cl3]2 3 6 6

[Pt(NH3)3Cl]2 [PtCl4] 3 6 6
Stereoisomerism

Co-ordination compounds which are having same molecular formula but

different orientation of ligands around central atom are known as
stereoisomers and this phenomenon is known as stereo-isomerism.
Assumptions

1. For monodentate ligands : a, b, c, d, ...........

Ex. [Pt(NH3)3(H2O)2Cl]3+ ⎯→ [Ma3b2c]

2. For symmetrical bidentate ligands : (AA)

Ex. [Pt(en)2(NH3)2]4+ ⎯→ [M(AA)2b2]

3. For unsymmetrical bidentate ligands : (AB)

Ex. [Cr(gly)3] ⎯→ [M(AB)3]
 Stereoisomerism for Square planar complexes

Sr. Geometrical Stereo- Optically Optically

Complexes E.P.
No. isomers isomers Inactive Active

1. [Ma4] Not Defined Not Defined 1 0 0

2. [Ma3b] Not Defined Not Defined 1 0 0

3. [Ma2b2] 2 2 2 0 0

4. [Ma2bc] 2 2 2 0 0

5. [Mabcd] 3 3 3 0 0

6. [M(AA)2] Not Defined Not Defined 1 0 0

7. [M(AA)2b2] Not Defined Not Defined 1 0 0

8. [M(AA)2bc] Not Defined Not Defined 1 0 0

 Stereoisomerism for Square planar complexes

Sr. Geometrical Stereo- Optically Optically

Complexes E.P.
No. isomers isomers Inactive Active

9. [M(AB)2] 2 2 2 0 0

10. [M(AB)c2] Not Defined Not Defined 1 0 0

11. [M(AB)cd] 2 2 2 0 0
 Example

The total number of possible isomers for square-planar

[Pt(Cl)(NO2)(NO3)(SCN)]2⊝ is :-
(1) 16 (2) 8 (3) 24 (4) 12

Solution [JEE (MAIN) 2018 Online]

Ans : (4)
 Example

The number of geometrical isomers that can exist for square planar
[Pt(Cl)(py)(NH3) (NH2OH)] is (py = pyridine) :
(1) 4 (2) 6 (3) 2 (4) 3

Solution [JEE (MAIN) 2015]

Ans : (4)
 Example

The number of geometrical isomers possible in triamminetrinitrocobalt

(III) is X and in trioxalatochromate (III) is Y. Then the value of X + Y
is _______.
[JEE (MAIN) 2021]

Solution

Ans : (2)
 Stereoisomerism
for
Tetrahedral Complexes
 Stereoisomerism for Tetrahedral complexes

(i) [Ma4]

(ii) [Ma3b]

(iii) [Ma2b2]
Geometrical Isomerism = Not Defined
(iv) [Ma2bc]
All are optically inactive
(v) [M(AA)2]
Stereoisomerism = not defined
(vi) [M(AA)b2]

(vii) [M(AA)bc]

(viii) [M(AB)c2]
 Stereoisomerism for Tetrahedral complexes

(ix) [Mabcd]
Geometrical Isomerism = Not Defined
(x) [M(AB)2] All are optically active

Stereoisomers = 2
(xi) [M(AB)cd]
 Stereoisomerism for Octahedral complexes
[A] For monodentate ligands

Sr. Geometrical Stereo- Optically Optically

Complexes E.P.
No. isomers isomers Inactive Active

1. [Ma6] Not Defined Not Defined 1 0 0

2. [Ma5 b] Not Defined Not Defined 1 0 0

3. [Ma4b2] 2 2 2 0 0

4. [Ma4bc] 2 2 2 0 0

5. [Ma3b3] 2 2 2 0 0

6. [Ma3b2c] 3 3 3 0 0

7. [Ma3bcd] 4 5 3 2 1

8. [Ma2b2c2] 5 6 4 2 1
[A] For monodentate ligands

Sr. Geometrical Stereo- Optically Optically

Complexes E.P.
No. isomers isomers Inactive Active

9. [Ma2b2cd] 6 8 4 4 2

10. [Ma2bcde] 9 15 3 12 6

11. [Mabcdef] 15 30 0 30 15
 [B] For symmetrical bidentate ligands

Sr. Geometrical Stereo- Optically Optically

Complexes E.P.
No. isomers isomers Inactive Active

1. [M(AA)3] Not Defined 2 0 2 1

2. [M(AA)2 b2] 2 3 1 2 1

3. [M(AA)2 bc] 2 3 1 2 1

4. [M(AA)b4] Not Defined Not Defined 1 0 0

5. [M(AA)b3c] 2 2 2 0 0

6. [M(AA)b2c2] 3 4 2 2 1

7. [M(AA)b2cd] 4 6 2 4 2

8. [M(AA)bcde] 6 12 0 12 6
 [C] For Unsymmetrical bidentate ligands

Sr. Geometrical Stereo- Optically Optically

Complexes E.P.
No. isomers isomers Inactive Active

1. [M(AB)3] 2 4 0 4 2

2. [M(AB)2c2] 5 8 2 6 3

3. [M(AB)2cd] 6 11 1 10 5

4. [M(AB)c4] Not Defined Not Defined 1 0 0

5. [M(AB)c3d] 3 4 2 2 1

6. [M(AB)c2d2] 4 6 2 4 2

7. [M(AB)c2de] 7 12 2 10 5

8. [M(AB)cdef] 12 24 0 24 12
 Example

The total number of possible isomers for [Pt(NH3)4Cl2]Br2 is ______.

[JEE Advance 2021]

Solution

Ans : (6)
 Example
Consider the following reaction and statements :
[Co(NH3)4Br2] Br⊝ → [Co(NH3)3Br3] + NH3
(I) Two isomers are produced if the reactant complex ion is a cis isomer.
(II) Two isomers are produced if the reactant complex ion is a trans-
isomer.
(III) Only one isomer is produced if the reactant complex ion is a trans-
isomer.
(IV) Only one isomer is produced if the reactant complex ion is a cis-
isomer.
The correct statements are :
(1) (I) and (III) (2) (III) and (IV)
(3) (II) and (IV) (4) (I) and (II)
Solution [JEE (MAIN) 2018 Offline]

Ans : (1)
 Example

Which one of the following complexes shows optical isomerism :-

(1) [Co(NH3)4Cl2]Cl (2) [Co(NH3)3 Cl3]
(3) cis[Co(en)2Cl2]Cl (4) trans[Co(en)2Cl2]Cl
(en = ethylenediamine)
[JEE (MAIN) 2016]
Solution

Ans : (3)
 Example

The correct option(s) regarding the complex Co en NH3 3 H2 O 3⊕ :-

(en = H2 NCH2 CH2 NH2 ) is (are) [JEE (Advance) 2018]
(A) It has two geometrical isomers
(B) It will have three geometrical isomers if bidentate 'en' is replaced by
two cyanide ligands
(C) It is paramagnetic
(D) It absorbs light at longer wavelength as compared to Co en NH3 4
3⊕

Solution

Ans : (A, B, D)
 Valence bond theory

This theory was mainly developed by Linus Pauling.

Linus Carl Pauling

Assumptions (1901-1994)
Nobel prizes: 1954, 1962

The central metal cation or atom makes available a number of vacant

s, p and or d-orbitals equal to its coordination number to form
coordinate covalent bonds with orbitals on the ligands.
Assumptions

These vacant atomic orbitals of metal are hybridized to form a new

set of equivalent bonding orbitals, called hybrid orbitals. These
orbitals are degenerate orbitals that is they have same energy.
Assumptions

The bonding in metal complexes arises when a filled ligand orbital

containing a lone pair of electrons overlaps with a vacant hybrid orbital
on the metal cation or atom to form a coordinate covalent bond

M ↿⇂ L M ↿⇂ L

Vacant metal Ligand orbital containing Coordinate covalent

hybrid orbital a pair of electron bond
Assumptions

The magnetic moment and the coordination number of the metal

cation or atom decide the hybridization and geometry of the
complex.

Strong ligands have the tendency to push and pair up the d-

electrons of metal cation or atom (pairing of electron does not
violate the Hund's rule of maximum multiplicity) and weak ligands
do not have the tendency to pair up the d-electrons.

In octahedral complexes, the central metal cation is either d2sp3

or sp3d2 -hybridized.
 EXAMPLE

Comment on hybridisation, geometry, and magnetic behavior of the

given complex
K4[Fe(Cl)6]

Solution

(Cl– is a monodentate ligand)

Electronic configuration of 26Fe :- [Ar] 3d64s2

So, Fe2+ :- [Ar] 3d64s0

3d 4s 4p 4d
↿
↿ ↿ ↿ ↿ ↿
 3d 4s sp4p
3d2 4d
↿⇂ ↿ ↿ ↿ ↿

Cl- Cl- Cl- Cl- Cl- Cl-

➢ Hybridisation (Fe) : sp3d2

➢ Geometry : Octahedral
➢ Unpaired electrons = 4
• Paramagnetic

• μ= n(n + 2) = 24 = 4.89 B.M

➢ Outer orbital complex

 EXAMPLE

Comment on hybridisation, geometry, and magnetic behavior of the

given complex
[NiCl4]2–

Solution

(Cl– is a monodentate ligand)

Electronic configuration of 28Ni :- [Ar] 3d84s2

So, 28Ni
2+ :- [Ar]18 3d8 4s0

3d 4s 4p
↿ ↿ ↿
↿ ↿ ↿ ↿ ↿
 3d 4s sp
4p3
↿⇂ ↿ ↿ ↿ ↿

Cl- Cl- Cl- Cl-

➢ Hybridisation (Ni) : sp3

➢ Geometry : Tetrahedral
➢ Unpaired electrons = 4
• Paramagnetic

• μ= n(n + 2) = 24 = 4.89 B.M

➢ Outer orbital complex

 Example

Comment on hybridization, number of unpaired electrons, outer or inner

orbital complex for the given complex [CoF6]3–

Solution

Ans.
• sp3d2
• Octahedral
• Paramagnetic
• Outer orbital complex
Limitations of VBT

It could not explain the nature of ligands i.e., which ligand is strong
and which one is weak.

It could not explain why the pairing of electrons occurs in the

presence of strong ligands.

From this theory magnetic moment can be calculated by knowing

the number of unpaired electrons but it could not explain the
effect of temperature on magnetic moment. It could also not
explain why the experimental value of magnetic moment is greater
than the calculated in some complexes.
Limitations of VBT

It could not explain the distortion in some octahedral complexes like

[Cr(H2O)6]2+.

It could not explain the colour and electronic spectra of complexes.

It could not explain reaction rates and mechanism of reactions of

complexes.

It could not explain the structure of [Cu(NH3)4]2+ ion.

 Crystal Field Theory

Assumptions

Central metal atom and ligands are treated as point charges.

There is purely ionic interaction between central metal atom and

ligands
 Crystal Field Theory for octahedral complex

Assumptions

Ligands approaches along the axes

When ligands approaches along the axes, then axial orbitals

feel more repulsion as compared to non-axial orbitals.

Hence, d-orbitals split into two sets i.e., ‘t2g’ and ‘eg’

t2g : dxy, dyz, dzx eg : d𝑥 2 − 𝑦 2 , d𝑧 2

 In other words, the energy of the eg orbitals increases much more than
the energy of the t2g orbitals.

eg

+0.6 ∆ O

Energy Barrycentre
ΔO
dxy dyz dx𝑧
xz dx2−y2 dz2

In presence of ligand –0.4 ∆ O

field, energy of d-
orbitals is increased

dxy dyz dxz dx2 −𝑦 dz2

−y2
t2g
d-orbitals of metal in
absence of ligand field ΔO = crystal field splitting energy of octahedral
Spectro-Chemical Series

− − −
I < B𝐫 < 𝐒തCN < Cl < S𝟐- < N𝐎𝟑 −

<
− − −
ഥ CS H2O CH3COO C2O42- OH F
< < < < <
𝐍

<
−
EDTA4- < NH3 < Py < en < dipy < N𝐎𝟐

<
−
CO CN
<
𝐍𝐨𝐭𝐞

−
1. From I to H2O ligands are known as weak field ligand (W.F.L.)

ഥ CS to CO ligands are known as strong field ligand (S.F.L.)

2. From N

3. C-donor atom > N-donor atom

(Strong field ligand.)

O-donor atom > Rest all

(Weak field ligand.)

4. C > N > O > Halogen (Rest all)

(Strong field ligand) (Weak field ligand)

Electronic configuration of (n-1)d e– after splitting depends
upon following two types of energy.

(1) O : Crystal Field splitting energy

(2) ‘P’ : Pairing Energy

In presence of SFL In presence of WFL

O > P O < P
 In presence of SFL In presence of WFL
O > P O < P

4 9 5 10
7 9 8 10
eg eg

1 6 2 7 3 8 4 9 5 10 1 6 2 7 3 8 4 9 5 10

(n-1)d (n-1)d

142536 162738
t2g t2g
Electron filling sequence in splitting diagram

dn configuration SFL ( > P) WFL (o < P)

d1 t2g1 eg0 t2g1 eg0

d2 t2g2 eg0 t2g2 eg0
d2 t2g3 eg0 t2g3 eg0
d4 t2g4 eg0 t2g3 eg1
d5 t2g5 eg0 t2g3 eg2
d6 t2g6 eg0 t2g4 eg2
d7 t2g6 eg1 t2g5 eg2
d8 t2g6 eg2 t2g6 eg2
d9 t2g6 eg3 t2g6 eg3
d10 t2g6 eg4 t2g6 eg4
 EXAMPLE

Comment on hybridisation, geometry, and magnetic behavior of the

given complex
K4[Fe(CN)6]

Solution

(CN– is a monodentate ligand and strong field ligand)

Electronic configuration of 26Fe :- [Ar] 3d64s2

So, Fe2+ :- [Ar] 3d64s0

3d 4s 4p 4d
↿
↿ ↿ ↿ ↿ ↿
After pairing due to presence of strong field ligand (CN–)

3d d4s
2sp3 4p 4d
↿⇂ ↿ ↿ ↿ ↿

CN- CN- CN- CN- CN- CN-

➢ Hybridisation (Fe) : d2sp3

➢ Geometry : Octahedral
➢ Unpaired electrons = 0
• Diamagnetic

• μ= n(n + 2) = 0 = 0 B.M

➢ Inner orbital complex

 Example

Which of the following complex ions has electrons that are symmetrically
filled in both t2g and eg orbitals ? [JEE (MAIN) 2015 Online]
(1) [CoF6]3⊝ (2) [Mn(CN)6]4⊝
(3) [FeF6]3⊝ (4) [Co(NH3)6]2

Solution

Ans : (3)
 Example

The pair having the same magnetic moment is :- [JEE (MAIN) 2016]
[At. No.: Cr = 24, Mn = 25, Fe = 26, Co = 27]
(1) [CoCl4]2⊝ and [Fe(H2O)6]2 (2) [Cr(H2O)6]2 and [CoCl4]2⊝
(3) [Cr(H2O)6]2 and [Fe(H2O)6]2 (4) [Mn(H2O)6]2 and [Cr(H2O)6]2

Solution

Ans : (3)
 Example

The correct order of spin-only magnetic moments among the following is:
(Atomic number : Mn = 25, Co = 27, Ni= 28, Zn = 30)
(1) [ZnCl4]2⊝ > [NiCl4]2⊝ > [CoCl4]2⊝ > [MnCl4]2⊝
(2) [CoCl4]2⊝ > [MnCl4]2⊝ > [NiCl4]2⊝ > [ZnCl4]2⊝
(3) [MnCl4]2⊝ > [CoCl4]2⊝ > [NiCl4]2⊝ > [ZnCl4]2⊝
(4) [NiCl4]2⊝ > [CoCl4]2⊝ > [MnCl4]2⊝ > [ZnCl4]2⊝

Solution [JEE (MAIN) 2018 Online]

Ans : (3)
 Factors Affecting
Crystal Field Splitting Energy
 Factors affecting Crystal Field Splitting Energy

Charge on metal ion

CFSE ∝ Charge on central atom with sign

Type of splitting

∆sq > ∆o > ∆t

Note

(i) ∆sq = 1.3 ∆o

4
(ii) ∆t = ∆o
9
 Type of metal ion

5d - metal ion > 4d metal ion > 3d metal ion

REASON :
In d - block, down the group, Zeff increases due to increase in poor
shielding electrons.

Type of ligands

Strong field ligand > Weak field ligand

Phenomenon of chelation

If donor atoms are same, then CFSE ∝ Number of rings formed by

ligands with metal ion.

Stability or CFSE of carbonyl complexes follows EAN rule or

Sidgwick rule only.
 Example

Compare stability of given complexes

1) K4[Fe(CN)6] K3[Fe(CN)6]

2) [CoCl6]4– [CoCl4]2–

3) [Co(NH3)6]3+ [Co(en)3]3+

4) [Co(NH3)6]3+ [Co(H2O)6]3+

5) [Co(H2O)6]3+ [Co(ox)3]3–

6) [Co(ox)3]3– [Co(en)3]3+

7) [NiCl4]2– [PdCl4]2– [PtCl4]2–

8) [Cr(CO)6] [Cr(CO)6]+

9) [Mn(CO)6] [Mn(CO)6]+
 Example
[JEE (MAIN) 2016 Online]
Identify the CORRECT trend given below :
(Atomic No. = Ti : 22, Cr : 24 and Mo : 42)
(1) ∆O of Cr H2 O 6
2+ < Mo H2 O 6
2⊕ and ∆O of Ti H2 O 6
3⊕ < Ti H2 O 6
2⊕

(2) ∆O of Cr H2 O 6
2⊕ < Mo H2 O 6
2⊕ and ∆O of Ti H2 O 6
3⊕ > Ti H2 O 6
2⊕

(3) ∆O of Cr H2 O 6
2⊕ > Mo H2 O 6
2⊕ and ∆O of Ti H2 O 6
3⊕ > Ti H2 O 6
2⊕

(4) ∆O of Cr H2 O 6
2⊕
> Mo H2 O 6
2⊕
and ∆O of Ti H2 O 6
3⊕
< Ti H2 O 6
2⊕

Solution

Ans : (2)
 Example

Which one of the following metal complexes is most stable ?

(1) [Co(en) (NH3)4]Cl2 (2) [Co(en)3]Cl2
(3) [Co(en)2(NH3)2]Cl2 (4) [Co(NH3)6]Cl2
[JEE (MAIN) 2021]
Solution

Ans : (2)
 Example

Arrange the following Cobalt complexes in the order of increasing

Crystal Field Stabilization Energy (CFSE) value.
Complexes : CoF6 3⊝
, Co H2 O 6
2⊕
, Co NH3 6
3⊕
and Co en 3
3⊕

A B C D
Choose the correct option :
(1) A < B < C < D (2) B < A < C < D
(3) B < C < D < A (4) C < D < B < A [JEE (MAIN) 2021]

Solution

Ans : (2)
Calculation of crystal field stabilization energy for octahedral complexes

eg

+0.6 ∆O
∆O
– 0.4 ∆O
t2g

CFSE = nt2g × (–0.4 ∆0) + neg × (0.6 ∆0) + xP

where, nt2g → number of electrons in t2g

neg → number of electrons in eg
P → Pairing energy
x → Number of electron pairs (forcefully)
 Crystal Field Theory
For
Tetrahedral Complexes
 t2

0.4 Δt
Energy
Δt
𝐝𝐱𝐲 𝐝𝐲𝐳 𝐝𝐱𝐳 𝐝𝐱𝟐−𝐲𝟐 𝐝𝐳𝟐

In presence of ligand –0.6 Δt

field, energy of
d-orbitals is increased e

𝐝𝐱𝒚 𝐝𝐲𝐳 𝐝𝐱𝐳 𝐝𝐱𝟐−𝒚𝟐 𝐝𝐳𝟐

In absence of ligand field d-orbitals of metal Δt = crystal field splitting energy of tetrahedral
 Crystal Field Theory
For
Square Planar Complexes
 Crystal Field Theory for square planar complexes
(Coordination number = 4)

9,10
d𝑥 2 − 𝑦 2
d𝑥 2 − 𝑦 2
d𝑥 2 − 𝑦 2 d 2
𝑧
7,8
d𝑧 2 dxy
o
sq
d𝑥𝑦 d𝑦𝑧 d𝑧𝑥 d 2 d 2 − 2 dxy
𝑧 𝑥 𝑦

5 ,6
dxy dyz dzx d𝑧 2
dyz dzx

1,3 2,4
dyz dzx
 EXAMPLE

Comment on hybridisation, geometry, and magnetic behavior of the

given complex
[Ni(CN)4]2–

Solution

(CN– is a monodentate ligand and strong field ligand)

Electronic configuration of Ni28 :- [Ar]18 3d84s2

So, Ni2+ :- [Ar]18 3d8 4s0

3d 4s 4p
↿ ↿ ↿
↿ ↿ ↿ ↿ ↿
After pairing due to presence of strong field ligand (CN–)

3d dsp
4s 2 4p
↿⇂ ↿⇂ ↿⇂ ↿ ↿

CN- CN- CN- CN-

➢ Hybridisation (Ni) : dsp2

➢ Geometry : Square planar
➢ Unpaired electrons = 0
• Diamagnetic

• μ= n(n + 2) = 0 B.M

➢ Inner orbital complex

 Example

The correct combination is [JEE (MAIN) 2018 Online]

(1) [Ni(CN)4]2⊝ – tetrahedral ; [Ni(CO)4] – paramagnetic
(2) [NiCl4]2⊝ – paramagnetic ; [Ni(CO)4] – tetrahedral
(3) [NiCl4]2⊝ – diamagnetic ; [Ni(CO)4] – square-planar
(4) [NiCl4]2⊝ – square-planar ; [Ni(CN)4]2⊝ – paramagnetic

Solution

Ans : (2)
 Example

Comment on hybridization, number of unpaired electrons, outer or inner

orbital complex and low or high spin complex for the given complex

[Cr(en)3]3+

Solution

Ans.
• d2sp3, Octahedral
• n=3
• Inner orbital complex
• Not defined
 Example

Comment on hybridization, number of unpaired electrons, outer or inner

orbital complex and low or high spin complex for the given complex

[Fe(CN)6]4–

Solution

Ans.
• d2sp3, Octahedral
• n=0
• Inner orbital complex
• Low spin complex
 Example

Comment on hybridization, number of unpaired electrons, outer or inner

orbital complex and low or high spin complex for the given complex

[Sc(H2O)6]Cl3

Solution

Ans.
• d2sp3, Octahedral
• n=0
• Inner orbital complex
• Not defined
 Example

Comment on hybridization, number of unpaired electrons, outer or inner

orbital complex and low or high spin complex for the given complex

[Ni(NH3)6]2+

Solution

Ans.
• sp3d2, Octahedral
• n=2
• Outer orbital complex
• Not defined
 Example

Comment on hybridization, number of unpaired electrons, outer or inner

orbital complex and low or high spin complex for the given complex

[Ti(H2O)6]2+

Solution

Ans.
• d2sp3, Octahedral
• n=2
• Inner orbital complex
• Not defined
 Example

Comment on hybridization, number of unpaired electrons, outer or inner

orbital complex and low or high spin complex for the given complex

[Co(en)3]Cl3

Solution

Ans.
• d2sp3, Octahedral
• n=0
• Inner orbital complex
• Low spin Complex
 Example

Comment on hybridisation, geometry, number of unpaired electrons,

and low or high spin complex for the given complex
K2[PtCl6]

Solution

Ans.
• d2sp3, Octahedral
• n=0
• Inner orbital complex
• Low spin complex
Conditions for transference of electrons

Central atom must be surrounded by all strong field ligands.

Only one electron can be transferred.

Inner orbital complex must be formed.

 Example

Comment on hybridization, number of unpaired electrons, outer or inner

orbital complex and low or high spin complex for the given complex

[Co(CN)6]4–

Solution

Ans.
• d2sp3, Octahedral
• n=1
• Inner orbital complex
• Low spin complex
Exceptions

Atomic number 24, 25, 26 and 27 with 6 NH3 in (+2) oxidation state
are exceptions.

Expected Real
Complexes Reason
hybridisation hybridisation

[Cr(NH3)6]2+ d2sp3 sp3d2 ∆o < P

[Mn(NH3)6]2+ d2sp3 sp3d2 ∆o < P

[Fe(NH3)6]2+ d2sp3 sp3d2 ∆o < P

[Co(NH3)6]2+ d2sp3 sp3d2 ∆o < P

Exceptions

All Co3+ complexes are d2sp3 hybridized except [CoF6]3– and

[Co (H2O)3 F3].

Complexes Hybridisation Reason

[Co(H2O)6]3+ d2sp3 ∆o > P

[Co(ox)3]3– d2sp3 ∆o > P
[Co(NH3)6]3+ d2sp3 ∆o > P
[Co(EDTA)]– d2sp3 ∆o > P
[Co(en)3]3+ d2sp3 ∆o > P
[Co(NO2)6]3– d2sp3 ∆o > P
[Co(CN)6]3– d2sp3 ∆o > P
 Example

Comment on hybridisation, geometry and number of unpaired electrons

for the given complexes

[CoCl4]2–

Solution

Ans.
• sp3
• Tetrahedral
• n=3
 Example

Comment on hybridisation, geometry and number of unpaired electrons

for the given complexes

Na2[Zn(OH)4]

Solution

Ans.
• sp3
• Tetrahedral
• n=0
 Example

Comment on hybridisation, geometry and number of unpaired electrons

for the given complexes

[MnO4] –

Solution

Ans.
• d3s
• Tetrahedral
• n=0
 Example

Comment on hybridisation, geometry and number of unpaired electrons

for the given complexes

[CrO4]2–

Solution

Ans.
• d3s
• Tetrahedral
• n=0
 Example

Comment on hybridisation, geometry, number of unpaired electrons, and

low or high spin complex for the given complexes

[Pd(PPh3)2Cl2]

Solution
 Example

Comment on hybridisation, geometry, number of unpaired electrons, and

low or high spin complex for the given complexes

[Ni(CN)4]2–

Solution
 Example

Comment on hybridisation, geometry, number of unpaired electrons, and

low or high spin complex for the given complexes

[Zn(gly)2]

Solution
 Example

Comment on hybridisation, geometry, number of unpaired electrons, and

low or high spin complex for the given complexes

[Co(en)2(NH3)2]3+

Solution
 Example

Comment on hybridisation, geometry, number of unpaired electrons, and

low or high spin complex for the given complexes

K3[Cu(CN)4]

Solution
 Example

Comment on hybridisation, geometry, number of unpaired electrons, and

low or high spin complex for the given complexes

[Ni(CO)4]

Solution
Various inner orbital octahedral complexes

Nature No. of
Complex Oxidation Valence Valence Bond Electrons
of Unpaired
Ion state shell E.C. Description
Ligands Electrons
3d 4s 4p

[Ti(H2O)6]3+ +3 3d1 weak 1

d2sp3-hybridization
3d 4s 4p

[V(H2O)6]3+ +3 3d2 weak 2

d2sp3-hybridization
3d 4s 4p

[Cr(H2O)6]3+ +3 3d3 weak 3

d2sp3-hybridization
3d 4s 4p

[Cr(CN)6]4– +2 3d4 strong 2

d2sp3-hybridization
 Various inner orbital octahedral complexes

Valence No. of
Complex Oxidation Nature of Valence Bond Electrons
shell Unpaired
Ion state Ligands Description
E.C. Electrons
3d 4s 4p

[Mn(CN)6]4– +2 3d5 strong 1

d2sp3-hybridization
3d 4s 4p

[Fe(CN)6]4– +2 3d6 strong 0

d2sp3-hybridization
3d 4s 4p
CN– → strong
[Fe(CN)5(NO)]2– +2 3d6 0
NO+→ strong
d2sp3-hybridization
3d 4s 4p

[PtCl6]2– +4 5d6 weak 0

d2sp3-hybridization
Various outer orbital octahedral complexes

Valence
Oxida
shell Nature No. of
Complex -tion
E.C. of of Valence Bond Electrons Description Unpaired
Ion state of
Metal Ligands Electrons
metal
Ion
3d 4s 4p

[Cr(H2O)6]2+ +2 3d4 weak 4

sp3d2-hybridization
3d 4s 4p

[Cr(NH3)6]2+ +2 3d4 strong 4

sp3d2-hybridization
3d 4s 4p

[Mn(H2O)6]2+ +2 3d5 weak 5

sp3d2-hybridization
3d 4s 4p
[FeF6]3–
or +3 3d5 weak 5
[Fe(H2O)6]3+
sp3d2-hybridization
Various outer orbital octahedral complexes

Valence
Oxida
shell Nature No. of
Complex -tion
E.C. of of Valence Bond Electrons Description Unpaired
Ion state of
Metal Ligands Electrons
metal
Ion
3d 4s 4p

[CoF6]3– +3 3d6 weak 4

sp3d2-hybridization
3d 4s 4p

[Co(NH3)6]2+ +2 3d7 strong 3

sp3d2-hybridization
3d 4s 4p

[Ni(NH3)6]2+ +2 3d8 strong 2

sp3d2-hybridization
Various tetrahedral complexes

Valence No. of
Oxidation Valence Bond Electrons
Complex Ion shell Unpaired
state Description
E.C. Electrons
3d 4s 4p
[MnX4]2–
+2 3d5 5
(X = Cl–, Br–)
sp3-hybridization
3d 4s 4p

[FeCl4]2– +2 3d6 4
sp3-hybridization
3d 4s 4p

[CoCl4]2– +2 3d7 3
sp3-hybridization
3d 4s 4p
[CuX4]2–
+2 3d9 1
[x = Cl–,Br–,CNS–)
sp3-hybridization
 Valence No. of
Oxidation Valence Bond Electrons
Complex Ion shell Unpaired
state Description
E.C. Electrons (n)
3d 4s 4p

[Cu(CN)4]3– +1 3d10 0
sp3-hybridization
3d 4s 4p
[ZnX4]2–
+2 3d10 0
[X = Cl–, Br–, I–]
sp3-hybridization
 Valence No. of
Oxidation
shell E.C. Valence Bond Electrons Unpaired
Complex state of
of Metal Description Electrons
metal
Cation (n)
3d 4s 4p

[Ni(dmg)2] +2 3d8 0
dsp2-hybridization

3d 4s 4p

[Cu(CN)4]2– +2 3d9 1

sp3-hybridization
 Valence Nu. of
Oxidation
shell E.C. Valence Bond Electrons Unpaired
Complex state of
of Metal Description Electrons
metal
Cation (n)
3d 4s 4p

[PdCl4]2– +2 4d8 0
dsp2-hybridization
3d 4s 4p

[PtCl4]2– +2 5d8 0
dsp2-hybridization
3d 4s 4p

[Pt(NH3)]2+ +2 5d8 0
dsp2-hybridization
 Example
The pair(s) of complexes wherein both exhibit tetrahedral geometry
is(are) (Note: py = pyridine)
Given: Atomic numbers of Fe, Co, Ni and Cu are 26, 27, 28 and 29,
respectively)
(A) [FeCl4]– and [Fe(CO)4]2⊝ (B) [Co(CO)4]⊝ and [CoCl4]2⊝
(C) [Ni(CO)4] and [Ni(CN)4]2⊝ (D) [Cu(py)4] and [Cu(CN)4]3⊝

Solution [JEE Advance 2021]

Ans : (A, B, D)
 Example

Match each set of hybrid orbitals from LIST-I with complex (es) given
in LIST-II.
LIST-I LIST-II
(P) dsp2 (1) [FeF6 ]4⊝
(Q) sp3 (2) [Ti(H2O)3Cl3]
(R) sp3d2 (3) [Cr(NH3 )6]3
(S) d2sp3 (4) [FeCl4]2⊝
(5) Ni(CO)4
(6) [Ni(CN)4]2⊝
The correct option is :-
(A) P → 5; Q → 4, 6; R → 2, 3; S → 1
(B) P → 5, 6; Q → 4; R → 3; S → 1, 2
(C) P → 6; Q → 4, 5; R → 1; S → 2, 3
(D) P → 4, 6; Q → 5, 6; R → 1, 2; S → 3
Solution
[JEE Advance 2018]

Ans : (C)
 Example

LIST-I contains metal species and LIST-II contains their properties.

LIST-I LIST-II
(I) [Cr(CN)6]4⊝ (P) t2g orbitals contain 4 electrons
(II) [RuCl6]2⊝ (Q) m(spin-only) = 4.9 BM
(III) [Cr(H2O)6]2 (R) low spin complex ion
(IV) [Fe(H2O)6]2 (S) metal ion in 4+ oxidation state
(T) d4 species
[Given : Atomic number of Cr = 24, Ru = 44, Fe = 26]
Metal each metal species in LIST-I with their properties in LIST-II,
and choose the correct option
(A) I → R, T; II → P, S; III → Q, T; IV → P, Q
(B) I → R, S; II → P, T; III → P, Q; IV → Q, T
(C) I → P, R; II → R, S; III → R, T; IV → P, T
(D) I → Q, T; II → S, T; III → P, T; IV → Q, R
Solution
[JEE Advance 2022]

Ans : (A)
 Example

The calculated spin only magnetic moments of [Cr(NH3)6]3 and [CuF6]3⊝

in BM, respectively, are (Atomic numbers of Cr and Cu are 24 and 29,
respectively)
(A) 3.87 and 2.84 (B) 4.90 and 1.73
(C) 3.87 and 1.73 (D) 4.90 and 2.84
[JEE Advance 2021]
Solution

Ans : (A)
 Example
In an experiment, m grams of a compound X (gas/liquid/solid) taken in a
container is loaded in a balance as shown in figure I below. In the presence
of a magnetic field, the pan with X is either deflected upwards (figure II),
or deflected downwards (figure III), depending on the compound X.
Identify the correct statement (s)
(A) If X is H2 O(l), deflection of the pan is upwards.
(B) If X is K 4 [Fe CN 6 ](s), deflection of the pan is upwards.
(C) If X is O2 (g), deflection of the pan is downwards.
(D) If X is C6 H6 (l), deflection of the pan is downwards.
(I) (II) (III)
Balanced ; Upward deflection ; Downward deflection ;
Magnetic field absent Magnetic field present Magnetic field present

m x
N S N S

magnet
Solution [JEE Advance 2020]

Ans : (A, B, C)
 Example

Choose the correct statement(s) among the following :

(A) [FeCl4]⊝ has tetrahedral geometry. [JEE (Advance) 2020]
(B) [Co(en)(NH3)2Cl2]⊕ has 2 geometrical isomers.
(C) [FeCl4]⊝ has higher spin-only magnetic moment than
[Co(en)(NH3)2Cl2]⊕.
(D) The cobalt ion in [Co(en)(NH3)2Cl2]| has sp3d2 hybridisation.

Solution

Ans : (A, C)
 Example

Among the species given below, the total number of diamagnetic species
is____.
H atom, NO2 monomer, O⊝
2 (superoxide), dimeric sulphur in vapour phase,
Mn3 O4 , NH4 2 [FeCl4 ], NH4 2 [NiCl4 ], K 2 MnO4 , K 2 CrO4
[JEE (Advance) 2018]
Solution

Ans : (1)
 Colour
in
Coordination Compounds
 Colour in Coordination compounds

(a) d-d transition

Mn+ L
eg

dxy dyz dxz dx2−y2 dz2

↿ t2g
 Note

In general, d0 and d10 electronic configurations are colourless and d1

to d9 are coloured.
 Example
Comment whether given species are coloured or not ?

(1) [Sc(H2O)6]3+

(2) Fe(CN)6]4–

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

(4) K3[Cu(CN)4]

(5) [Cu(NH3)4] SO4

(6) [Cr(H2O)6]3+

(7) Na2[Zn(OH)4]

(8) MnO–4

Solution
 Colour in Coordination compounds

(b) Charge transfer

There are some compound in which central metal atom is d0 but

coloured due to charge transferred from ligand to metal ion

MnΟ−
4

CrO2−
4

Cr2Ο2−
7
All are
3d0 d3s hybridised and they are coloured
CrO2Cl2

CrO2F2

VO3−
4

MnO2−
4 3d1
Complementary Colour Wheel

𝜆maximum
Eminimum
𝜆minimum
Emaximum

E↓
 Example

Two complexes, [Cr(H2O6)]Cl3 (A) and [Cr(NH3)6]Cl3 (B) are violet and
yellow coloured, respectively. The incorrect statement regarding them is:
(1) 0 value of (A) is less than that of (B).
(2) 0 value of (A) and (B) are calculated from the energies of violet and
yellow light, respectively
(3) Both absorb energies corresponding to their complementary colors.
(4) Both are paramagnetic with three unpaired electrons.
[JEE (MAIN) 2019]
Solution

Ans : (2)
 Example

Among the statements(a)-(d), the incorrect ones are-

(a) Octahedral Co(III) complexes with strong field ligands have very
high magnetic moments
(b) When Δ0 < P, the d-electron configuration of Co(III) in an
octahedral complex is t4eg e2g
(c) Wavelength of light absorbed by [Co(en)3]3 is lower than that of
[CoF6]3⊝
(d) If the Δ0 for an octahedral complex of Co(III) is 18,000 cm–1, the
Δt for its tetrahedral complex with the same ligand will be 16,000
cm-1
(1) (a) and (b) only (2) (c) and (d) only
(3) (b) and (c) only (4) (a) and (d) only
Solution [JEE (MAIN) 2020]

Ans : (4)
 Example

[Co2(CO)8] displays :- [JEE (MAIN) 2017 Online]

(1) No Co-Co bond, four terminal CO and four bridging CO
(2) One Co-Co bond, six terminal CO and two bridging CO
(3) No Co–Co bond, six terminal CO and two bridging CO
(4) One Co-Co bond, four terminal CO and four bridging CO

Solution

Ans : (2)
 Example
Match each coordination compound in List-I with an appropriate pair of
characteristics from List-II and select the correct answer using the code given
below the lists.
{en = H2NCH2CH2NH2 ' atomic numbers ; Ti = 22 ; Cr = 24 ; Co = 27 ; Pt = 78}
List-I List-II
(P) [Cr(NH3)4Cl2]Cl (1) Paramagnetic and exhibits ionisation isomerism
(Q) [Ti(H2O)5Cl](NO3)2 (2) Diamagnetic and exhibits cis-trans isomerism
(R) [Pt(en)(NH3)Cl]NO3 (3) Paramagnetic and exhibits cis-trans isomerism
(S) [Co(NH3)4(NO3)2]NO3 (4) Diamagnetic and exhibits ionisation isomerism
Code :
P Q R S
(A) 4 2 3 1
(B) 3 1 4 2
(C) 2 1 3 4
(D) 1 3 4 2
Solution [JEE (Advance) 2014]

Ans : (B)
On the basis of electron pair donating and accepting tendency

Classical ligands

L Central atom

••
LIGANDS

Non-Classical ligands

L Central atom

••
π*
(vacant)
 EXAMPLE


CO, CN, N2, NO+, NO ……… σ-donor, π-acceptor

*ABMO present to accept e– from metal

PH3, PF3, PCl3, PEt3, PPh3, ……… σ-donor, π-acceptor

Vacant d-orbitals are present to accept e–

from metal

C2H4, π – C3H5–, π – C5H5, π – C6H6 …π-donor, π-acceptor

Vacant *ABMO present to accept e– from

metal
 Synergic bonding


– + + – – –
M 
C  O: M C  O:
+ – – + + +

(d orbital of CMA) *(ABMO) of CO ( coordinate bond)

When negative charges on Central metal atom increases then tendency

of CMA to donate electron pair increases. Thus extent of synergic
bonding (Back bonding) increases.

When increasing number of electrons in vacant * (ABMO) of CO then

(C-O) Bond order (↓) bond length (↑) bond strength (↓)
 bonding in carbonyl compounds (Synergic bonding)

 - back bond from metal to vacant orbital of CO makes CO electron

rich or makes it better lone pair donor. Similarly,  - donation from
CO to metal makes metal electron rich so metal’s lone pair donating
tendency to CO increases. (synergizing effect)

- –
+

M C O

+ - –

(d orbital of CMA) (ABMO) of CO

 Synergic bonding

When negative charge increases on CMA then back donation from

metal to ligand increases so double bond character between metal
and ligand increases.
(M-C) bond order (↑) bond strength (↑) bond length (↓)
Before S.B. :

– +
C.A. C≡O

••
••
σ

During S.B. :

(S.B)
𝜋∗
𝜋 +
–
C.A. σ C ≡O

••

••
After S.B. :

π +
–
C.A. σ C == O
After S.B. :

π +
–
C.A. σ C == O

Bond Order ↑ Bond Order ↓

Bond Length ↓ Bond Length ↑

Bond Strength ↑ Bond Strength ↓

Note

Synergic bonding ∝ electron density on central atom

EXAMPLE

[M(CO)x]+ [M(CO)x]0 [M(CO)x]–

When we move from left to right electron density on CMA (↑)

Back donation (↑)

Extent of synergic bonding (↑)

 Example

Strongest C—O bond is present in

(1) [Cr(CO)6]+
(2) [V(CO)6]-
(3) [Fe(CO)5]
(4) Same in all

Solution
 Example

In [Fe(CO)5] complex, the Fe – C bond possesses

(A) Ionic character (B) 𝜎- character only
(C) 𝜋 – Character only (D) Both 𝜎 and 𝜋 - character

Solution
 Example

The bond length between carbon and oxygen in CO molecule is 1.128 Å

then what will be the dc-o in [Fe(CO)5] ?
(A) 1.128 Å (B) 1.72 Å
(C) 1.115 Å (D) 1.15 Å

Solution
 Example

In the following complexes, the maximum C — O bond length in :

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

Solution
 Example

Bond length order : dC – C (C2H4) dC – C (Zeise’s Salt)

Solution
 Example

Low oxidation state of metals in their complexes are common when

ligands :
(A) have good -accepting character [JEE (MAIN) 2022]
(B) have good -donor character
(C) are having good -donating ability
(D) are having poor -donating ability

Solution

Ans : (A)
 Example
The correct statement(s) regarding the binary transition metal
carbonyl compounds is (are) [JEE (Advance) 2018]
(Atomic numbers : Fe = 26, Ni = 28)
(A) Total number of valence shell electrons at metal centre in
Fe CO 5 or Ni CO 4 is 16
(B) These are predominantly low spin in nature
(C) Metal - carbon bond strengthens when the oxidation state of the
metal is lowered
(D) The carbonyl C–O bond weakens when the oxidation state of the
metal is increased

Solution

Ans : (B, C)