INORGANIC CHEMISTRY : V.K.

JAISWAL(VKJ SIR)

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.

Classification of Ligands

(I) (II) (III )

On the basis of charges On the basis of Denticity
- Negative ligands - Mono/Unidentate ligands
- Neutral ligands - Bi/Didentate ligands
- Poly/Multidentate ligands
- Positive ligands
- Ambidentate ligands
(Must be –ve ligand with
2 different donar atoms)
–
On the basis of e pair donating &
accepting tendency
 L)
- Classical (normal) lignads (M

- Non classical (-acid) ligands(M  L)

Negative Ligands : Carry negative charge

– – –
H : Hydride SCN : Thiocyanate CH3COO : Acetate
– –
F : Flouride NCS : sothiocyanate C2O4
2–
: Oxalate
– 2–
Cl : Chloride SO4 : Sulphate 2–
– 2–
CO3 : Carbonate
Br : Bromide SO3 : Sulphite –
I
–
: Iodide 2–
CH3 : Methyl
S2O3 : Thiosulphate –
O2
2–
: peroxide –
CH3CH2 : Ethyl
N3 : Azide –
O2
–
: Superoxide 3–
C6H5 : Phenyl
2– N : Nitride SnCl3
–
: Trichlorostannite
O : Oxide NH2
–
: Amide –
– C5H5 : Cyclopentadienyl
OH : Hydroxide NH
2–
: mide
– –
CH3O : Methoxide – CH2 = CH – CH2 : Allyl
NO2 : Nitrite
(I) On the Basis of charges

–
OCN : Cyanate NO3
–
: Nitrate
–
NCO : socyanate CN
–
: Cyanide
–
NC : Isocyanide

Neutral ligands : Carry no charge

e.g. NH3 (Ammine), H2O(Aqua), CO (Carbonyl), NO(Nitrosyl), O2(Dioxygen), N2(Dinitrogen),

PH3(Phosphene), PMe3(Trimethyl phosphene), PPh3(Triphenyl phosphene), N2H4(Hydrazine),
MeNH2(Methyl amine), EtNH2(Ethyl amine), R2O(Normal ether), R2S (Thio ether),

,
N
(Pyridine) (Benzene)

Positive ligands : Carry positive charge

+
e.g. N2H5 : Hydrazinium.
+
NO : Nitrosylium or Nitrosonium

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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.

Monodentate ligands :
– – 3–
H : Hydride CH3O : Methoxide N : Nitride
F
–
: Flouride Me2O : Dimethyl ether NH3 : Ammine
– –
Cl : Chloride Me2S : Dimethyl thioether NH2 : Amide
– – 2–
Br : Bromide OCN : Cyanate NH : mide
– –
I : Iodide NCO : socyanate H2N – NH2 : Hydrazine
2– – –
O : Oxide SCN : Thiocyanate NO2 : Nitrite-N
2– – –
O2 : Peroxide NCS :  sothiocyanate ONO : Nitrite-O
– 2– –
O2 : Superoxide SO4 : Sulphate NO3 : Nitrate
2–
OH
–
: Hydroxide S O3 : Sulphite C5H5N : Pyridine
2– –
(II) On the Basis of Denticity

O2 : Dioxygen S2O3 : Thiosulphate CH3COO : Acetate

– 2–
H2O : Aqua N3 : Azide CO3 : Carbonate
–
CO : Carbonyl NO : Nitrosyl SnCl3 : Trichlorostannite
–
CN : Cyanide
–
NC : Isocynide
(Underlined Atoms are donar site of ligands.)
2– 2– 2– – – – 2–
Among these monodentate ligands, some ligands like SO3 , SO4 , S2O3 , NO2 , NO3 , CH3 COO , CO3
can also act as bidentate ligands, therefore these ligands are also called flexidentate ligands because
of their variable denticity. Such monodentate ligands form lessstable four membered ring when they act as
bidentate ligands however their preferred denticity is one.

O 2– CH3 O 2– 2–
O
C C S S
– N+ N
O O O O – –
O O O (–)
O O O O O
O O
M M
M M M M
Carbonate Acetate Nitrate Nitrite Sulphate Sulphite

–
Polydentate ligands : Such ligands are capable of donating two or more lone pair e s to same central
metal atom/ion through co-ordinate bonds. While doing so they form 5/6 membered stable ring. Hence
such ligands are also called chelating ligands.

Bidentate Ligands : Having two donor atoms/coordination sites.

H2
– N
O O M
C H2C
N N
M M
H2C N N
C
–
O O N M
Oxalate (ox) H2 Dipyridine (dipy) Phenanthrolene (phen)
(Symmetrical ligand) Ethylenediamine (en) (symmetrical ligand) (Symmetrical ligand)
(symmetrical ligand)

H2 Me Ph
N C O
C O
H2C HC M
M HC M –
C
– C O
C O
– Me Me
O O
Glycinate (gly) Acetylacetonate (acac) Benzoylacetonate (bcac)
(unsymmetrical ligand) (symmetrical ligand) (unsymmetrical ligand)

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 PMe2
H2C H3C CH3
M * * H2C — CH — CH3
CH — CH
H2C | | | |
H2N NH2 H2N NH2
PMe2 M
M
1, 2 bis (dimethylphosphino) Propylenediamine(pn)
Butylenediamine(bn)
ethane. (dmpe) (unsymmetrical ligand)
(symmetrical ligand)
(symmetrical ligand)
2NH4OH (Basic Mdm.)
NiCl2 + 2DMG –2H2O
[Ni(DMG)2]
(Rosy Red ppt.)
–
O–H---O In DMG donor sites are both
H3C — C N N-atoms rather than one O
2+ N = C — CH3
Ni and one N-atom because
H3C — C N in this case formed complex
– N = C — CH3 get extra stability due to
O - - H–O formation of additional
bis (dimethylglyoximato)nickel(II) stable rings through H-bonds.
Number of formed rings = 4
2 rings : 5 membered
2 rings : 6 membered
• 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
Types of Polydentate Ligands

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

H CH2 — CH2
N
NH2
H2C M
H2C
N
H2
Diethylenetriamine (dien)

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

H CH2 — CH2
N H
N
H2C CH2
M
H2C
CH2
N N
H2 H2
Triethylenetetraamine (trien)
(iii) Pentadentate ligand :
H H H
H2N – CH2CH2 – N – CH2CH2 – N – CH2 CH2 – N – CH2 CH2 – NH2

M
tetraethylenepentaamine (teten)

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 (iv) Hexadentate Ligand :
CH2COOH
N
–
H2C CH2COOH OH 4–
H4 EDTA EDTA
H+
H2C (water insoluble) (water soluble)
CH2COOH
N Ethylenediaminetetraacetic acid Ethylenediaminetetraacetate
CH2COOH
(H4EDTA)
Flexidentate character of EDTA4– at different pH value

Ligands Denticity
H4EDTA 2
–
H3EDTA [ethylenediamineacetate] 3 As pH of solution decreases
2– 4–
H2EDTA [ethylenediaminediacetate] 4 denticity of EDTA also decreases
3–
HEDTA [ethylenediaminetriacetate] 5
4–
EDTA [ethylenediaminetetraacetate] 6
* EDTA4– always gives octahedron geometry due to six coordinaion sites.

O O
– 2–
O
– 2–
C
CH2 O
CH2 C
–
No. of N – Ca – N Bond angles = 1 N O –
H2C N O
+2
No. of O – Ca – O Bond angles = 6 Ca +2
OR Ca
H2C –
No. of N – Ca – O Bond angles = 8 N O –
N O
CH2 C
CH2
O
–
C—O –
O
O
2–
[Ca(EDTA)]
2– [Ca(EDTA)]

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.
–
M  SCN : Thiocyanate - S
–
M NCS : Thiocyanate - N
–
M OCN : Cyanate These ambidentate Ligands
–
M NCO : Isocyanate show monodentate behaviour.
–
M CN : Cyanide
–
M NC : Isocyanide
–
M  NO2 : Nitrite - N
–
M ONO : Nitrite - O
2–
M S2O3 : Thiosulphate -S
2–
M OS2O2 : Thiosulphate - O
2–
M SO3 : Sulphite - S These ambidentate Ligands can also show
M OSO2
2–
: Sulphite - O flexidentate behaviour as they are Non-linear.
–
M NOS : Thionitrite - N
–
M ONS : Thionitrite - O
–
M SNO : Thionitrite - S

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

Ligands

 /
Classical Ligands (M L) Non classical Ligands (M
(Normal ligands)  L)

When ligands can only donate their lone pair ( - acid /  - acceptor ligand)
to the vacant orbital of the central metal
When ligands donate their lone pair to the vacant
atom/ion through coordinate bond are called
classical (normal) ligands. orbital of central metal atom/ion and simultaneously
– – – 2– – – accept electron pair from filled d-atomic orbital of
eg. H , OH , NH3, H2O, NH2 , NH , F , CH3 ,
–
central metal atom/ion through back bond either
C2H5 , MeNH2
into vacant atomic orbital of donor atom or into
Types of Complexes : * MO of ligand are called non-classical (-acid)
On the basis of M – L interaction ligands.
complex compounds are of three types
(i) -Bonded complex compound :

(Having M L interaction)
donation 
3– + 3+

eg. [FeF6] , [Ag(NH3)2] , [Fe(H2O)6] M L M L
 
R – Mg – X, Zn(C2H5)2, Pb(C2H5)4(TEL) Ligands of such Ligands of such
category are : category are :
-Bonded OMC +
CO, NO, NO , N2, 2 - CH2 = CH2 (-ethene)
(ii) and -bonded complex compound PPh3, PF3, CN
– 6 - C6 H6 (-benzene)
–
-allyl, -cyclopentadienyl 5 - C5H5 (-cyclopentadienyl)
-donation –
(Having M  3 - CH2 = CH – CH2 (-allyl)
  L interaction)
-acceprance 4 - CH2 = CH – CH = CH2 (-butadiene)
4– –
eg. M(CO)x , [Fe(CN)6] , [Ag(CN)2]
Organometallic Compound : OMC are type of complex
OMC
(iii) -bond complex compound compunds with metal carbon linkage (M  C linkage)

-donation where M : mostly metal / may be non-metal

(Having M 
L interaction) or metalloid with less EN value than carbon and
-acceprance C atom is of alkyl/aryl group including CO
5
eg. Cr(C6H6)2 , Fe( -C5H5)2 , K[PtCl3( – C2H4)]
2 NOTE : All OMC are complex compound but all
(ferrocene) (Ziese's salt) complex compounds are not OMC.

-Bonded OMC

IMPORTANT POINTS REGARDING LIGANDS

1. NH4+ cation never act as ligand.
2. Metal cation with +3 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).
– Bridging ligand
X

M M
4. Neutral ligands in which two different atoms are having lone pairs, then preferential donor site is less
electronegative atom eg. CO, NO.
5. 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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