CO-ORDINATION COMPOUND

Double Salt or Lattice Compounds

The addition compounds which loose their identity in aq. Solution and get
completely ionized in water.
• Ex. K2SO4.Al2(SO4)3. 24H2O. (Potash Alum)

• KMgCl3·6(H2O) (Carnallite).

• FeSO4(NH4)2SO4. 6H2O (Mohr's Salt).

Coordination or Complex Compounds

Complex retain their identity in aqueous solution. i.e., they do not dissociate into
separate ion.

Potassium ferrocyanide Ferrocyanide ion

 Central metal ion Coordination sphere

Spectator ion

Ligand Coordination number

On the basis of type of ligands complex compounds are divided as follows :

(1) Homoleptic complexes : Complex in which all the ligands are identical is called homoleptic complex.
Ex. [Co(NH3)6]+2
(2) Heteroleptic complexes : Complex in which all the ligands are not identical is known as heteroletic
complex.
Ex. [Fe(en)2Cl2]+1
Terminology
(a) Complex Ion :- An aggregate of metal ion with anions, cation or neutral molecules is called as complex ion.
(b) Central Metal Ion :- Central metal ion acts as an electron pair acceptor and forms coordinate covalent bond.
(c) Coordination Number :- The total number of coordinate covalent bonds formed by central metal ion with
ligands is called as coordination number.
(d) Oxidation State :- It is a number which represents the electrical charge on the central metal atom of a
complex ion.
Ex. The oxidation number of Fe, Co and Ni in [Fe(CN)6]4-, Co(NH3)6]3+ and Ni(CO)4 is +2, +3
and zero respectively.
(e) Ligands :- The anions, cation or neutral molecules which combine with central metal
ion to form complex ion are called as ligands.

Negatively Charged Ligand

Neutral Ligand

Positively Charged Ligand

(f) Naming of Ligands :-

(1) O- suffix is provided to the name of anionic ligands. Ex. Clorido , Bromido, Cynido.

(2) ium-suffix is provided to the name of cationic ligands. Ex. Hydrazinium.

Denticity :- No. of lone pair donated to central metal atom to form
coordinate bonds.

Classification of ligands : On the basis of denticity:

1. Monodentate Ligand : Which has only one donor site or which can donate only one lonepair.
Neutral monodentate ligands : Cationic monodentate ligand : Anionic monodentate ligands :
NH3 ammine NO+ nitrosylium or nitrosonium F- Fluorido/fluoro
H2O aqua 𝑵𝑶+ 𝟐 nitronium Cl- Chlorido/chloro
NO nitrosyl H2N-N+H3 hydrazinium Br- Bromido/bromo
PH3 phosphine I- iodido/iodo
PPh3 triphenyl phosphine O-2 oxido/oxo
O2 dioxygen S-2 sulphido/sulpho
N2 dinitrogen OH- hydroxido/hydroxo
CH3-OH methyl alcohol CH3-O- methoxido/methoxo
CH3-NH2 methyl amine 𝑶− 𝟐 superoxido/superoxo
NH2CONH2 urea 𝑶−𝟐𝟐 peroxide/peroxo
NH2NH2 hydrazine N- nitrido
CH3-O-CH3 dimethyl ether 𝑵𝟑− azido
CO carbonyl (NH2)- amido
CS thiocarbonyl NH-2 imido
H- hydrido
2. Bidentate ligands : Ligands which has two donor sites (simultaneously)

3. Polydentate ligands : Which donates more than two lone pair to central metal atom to
form coordinate bond.

Hexadentate ligand

Ethylenediaminetetraacetate
4. Ambidentate ligand : Ligands which have two different donor atoms but at the
time of coordination can donate electron pair from any one donor atoms are called
ambidentate ligand.

5. Flexidentate ligands : Ligands which can change their denticity.

𝑺𝑶𝟒−𝟐 , 𝑪𝑶−𝟐
𝟑 etc are generally act as monodentate ligand but in some compound
they can act as bidentate ligand.

Eg.
(1) [Co(NH3)5(SO4)]Cl in this complex 𝑺𝑶−𝟐
𝟒 act as a monodentate ligand.

(2) [Co(NH3)4(SO4)]Cl in the complex 𝑺𝑶𝟒−𝟐 act as a bidentate ligand.

6. Chelating Ligands : Bidentate or polydentate ligands which attach themselves
with central metal ion in such a way that they form a ring, are known as chelating ligands.
No. of rings = denticity – 1

5 or 6 membered rings are more stable

On the basis of nature between central metal atom and ligand.

(1) Normal or classical ligands

(2) Non classical or 𝝅-acid or 𝝅 −acceptor ligands

(1) Normal or classical ligands : (𝝈 − 𝒅𝒐𝒏𝒐𝒓)

For Ex. :- H2O, Cl-, Br-

(2) Non classical or 𝝅-acid or 𝝅 −acceptor ligands

𝝅 – acid ligands -------> CO, CN-

,N𝑶−𝟐
Synergic Bonding :- Stronger the 𝝈-bond, stronger is the 𝝅-bond.
 IUPAC NOMENCLATURE OF COORDINATION COMPOUNDS

The present system of nomenclature derived from the suggestions of Alfred Werner and
recommended by the Inorganic Nomenclature Committee of the I.U.P.A.C. The main rule of
naming of complexes are :-

(a) First cation is written then anion.

 (b) In coordination sphere first ligands are written in
alphabetical order then Central metal atom.

• ‘ide’ is replaced by ‘ido’.

• ‘ate’ is replaced by ‘ato’.
• ‘ite’ is replaced by ‘ito’.

𝑪𝑶−𝟐
𝟑 Carbonato 𝑺𝑶−𝟐
𝟑 Sulphito
𝑪𝟐 𝑶−𝟐
𝟒 Oxalato (Ox)
-2 CH3COO- Acetato
S𝑶−𝟐
𝟒 Sulphato N𝑶−𝟐 (bonded through oxygen) nitrite
N𝑶−𝟑 Nitrato -------------> Nitrito – N
(bonded through nitrogen) nitro Nitrito - O
(C) If same ligand is present than once then use prefix :-

2 – di
3 – tri
4 – tetra
5 – penta
6 – hexa [Co(NH3)6]Cl3 -------------------> HexammineCobalt(3)Chloride

(d) After writing ligands, central metal atom is written along with oxidation number.

(e) If coordinate sphere is anionic then central metal atom name ends with –ate.

Cr -----> Chromate Au -------> Aurate Cu --------> Cuprate

Zn -----> Zincate Ni --------> Nickelate Fe --------> Ferrate
Ag-----> Argentate Pb --------> Plumbate
Iupac name :- H[AuCl4] ---------------> Tetra chloride auric(3)acid
H+ ----> spectator ion

H2[PtCl6] --------------> Hexachloroplatinic(4)acid

[Fe(H2O)5NO]SO4 -----------> Pentaaquanitrosoniumiron(1)sulphate

Na2[Fe(CN)5NO] ------------> Sodium pentacyanonitrosonium ferrate(2)

Most common oxidation state of

Ni, Pd, Pt ---------> 2,4

Cu, Ag ------------> 1,2
Sn,Pb ------------> 2,4
Co, Fe ------------> 2,3
Au ----------------> 1,3
Cr -----------> 3

Ex. : - (1) [Pt(NH3)4Cl2][PtCl4] -------------->

Tetramminedichloridoplatinum(4)tetrachloridoplatinate(2)
How to write formula of coordination compound :-
Spectator ion [ Central metal atom –ligands in alphabetical order]Spectator ion (anion)
(Cation)

Q. Potassium hexacyanidoferrate(2). Write the formula ???

 Bonding in Coordination compounds
(A) Werner’s Theory

• According to Werner central metal have 2 types of valencies :

• Primary valencies Secondary valencies

(1) Equal to oxidation state of Central metal atom (1) Equal to coordination number of central metal atom
(2) Satisfied by anions (2) Satisfied by ligands
(3) Non directional (3) Directional
(4) Ionisable (4) Non-ionisable
(5) Not helpful geometry predictions (5) Helpful in geometry predictions
(6) Negatively charged ion (6) Neutral or negatively charged ions.

Shapes :- According to werner all secondary valencies has shapes arrangement according to coordination
number.
 Co(NH3)6Cl3 + excess AgNO3 ------------------------> 3 Moles AgCl p.p.t

Co(NH3)6Cl3 + excess AgNO3 ------------------------> 2 Moles AgCl p.p.t

Co(NH3)6Cl3 + excess AgNO3 ------------------------> 1 Moles AgCl p.p.t

Co(NH3)6Cl3 + excess AgNO3 ------------------------> No p.p.t

Experimental evidence of werner’s theory
(a) Precipitation of primary valencies on the addition of a suitable reagent.

Ex. Fe(NH3)6Cl3 forms 3 moles of AgCl in the form of precipitate on addition of

AgNO3.

Fe(NH3)6Cl3 -----------------> [Fe(NH3)6]+3 + 3Cl-

(b) Electrical conductance of complexes : Electrical conductivity 𝜶 No. of ions.

Ex. The electrical conductance of aqueous [Fe(NH3)6]Cl3 is greater than that of

aqueous solution of [Fe(NH3)5Cl]Cl2.

[Fe(NH3)6]Cl3 -----------------> [Fe(NH3)6]+3 + 3Cl- Total number of ions = 4

[Fe(NH3)5Cl]Cl2 -----------> [Fe(NH3)5Cl]+2 + 2Cl- Total number of ions = 3

Effective Atomic Number :- (E.A.N.)

E.A.N. = total number of electron + (2 x number of coordinate

bonds)
in central metal atom/ion

Q. Find the E.A.N. of

(a)Ni(CO)4
(b)[Cr(NH3)6]Cl3

Ans. :- (a) EAN = 28 + (2x4) = 36

(b) EAN = (24-3) + (2x6) = 33

• If E.A.N. of central metal atom/ion is equal to noble gas

configuration (2,10,18,36,54,86,118) then it is stable compound.
Applications of E.A.N. :-

(a) Whether compound act as an oxidising agent or reducing agent

• [V(CO)6] + 1e- -----------------> [V(CO)6]-

EAN :- 23 + 2x6 = 35 EAN :- 36 (Noble gas configuration)

SO, it reduce itself and act as an oxidising agent.

• [Mn(CO)6] --------------------> [Mn(CO)6]+ + 1e-

EAN :- 25 + 2x6 = 37

So, it will oxidise itself and act as reducing agent.

(b) Whether compound exist as mononuclear or poly nuclear

Ex. :- [Co(CO)4] EAN = 27 + 2x4 = 35 so, not completely stable.

So, it will exist in [Co2(CO)8] EAN = 36

(C) Whether M-M bond exist or not :-

[Co2(CO)8] EAN of 2 Co = 54 + 2x8 = 70

EAN of 1 Co = 35
So, to get 36 EAN one metal- metal must be present
VALENCE BOND THEORY

• This theory was mainly developed by Linus pauling. The main

features of this theory are :-
• Central metal atom electronic configuration ion in ionic state.

• Ligand (a) Strong ligand  pairing of C.M.A e- if possible

(b) Weak ligand  No pairing of C.M.A e-.

• Now ligand will form coordinate bond.

• Paramagnetic :- due to presence of unpaired electrons.

• Diamagnetic :- All electrons are paired.

• 𝝁= 𝒏 𝒏+𝟐 1/2 𝝁 = magnetic moment

n = Number of unpaired electrons.
#Behaviour of Ligand :-

(a) 3d series metals in M+2 :- X-<H2O<NH3<CN-<CO<NO+

Weak ligand Strong ligand

(b) 3d series metals in M+3 :- X-<H2O<NH3<CN-<CO<NO+

Weak ligand Strong ligand

(c) M ≥ +4 OR 4d, 5d series metal :- All ligands act as strong ligand.

 Coordination number :- 6

Octahedral

• Sp3d2 • d2sp3
• Outer orbital complex • Inner orbital complex
• High spin complex • Low spin complex
• Ligand weak • Ligand strong
• Pairing of central metal atom electrons • Pairing of central metal atom electrons take
will not take place. place and 2 orbitals will be empty if possible.
• Ex. :- H2O, X- • Ex. :- CO, CN-, and 𝝅 −acid ligands.
Q. Explain Hybridization, structure, magnetic moment and magnetic
character of
(A) [Ni(H2O)6]+2.
Ans:-
(B) [Fe(CN)6]4-
 Coordination Number :- 4

Tetrahedral square planner

• Sp3 • dsp2
• Outer orbital complex • Inner orbital complex
• High spin complex • Low spin complex
• Ligand weak
• Ligand strong
Q. Find hybridization, structure, magnetic moment and magnetic character of

(a) [Ni(CN)4]-2
(b) [Ni(CO)4]
(c) [PdCl4]2-
 ISOMERISM IN COMPLEXES
• Compounds which have the same molecular formula, but differ in their properties.
(1) Structural Isomerism

(a) Ionisation Isomers :-

• The type of isomerism which is due to the exchange of groups or ion between the
coordinating sphere and the ionisation sphere.
• Ex. :- Co(NH3)4Br2SO4 can represent
(A) [Co(NH3)4Br2]SO4 (B) [Co(NH3)4SO4]Br2 (red).

• These complex give sulphate ion and bromide ion respectively.

(b) Hydrate Isomers :-

• This type of isomerism is due to presence of different number of water

molecules inside a coordinate sphere.
• Ex. :- (A) Cr(H2O)6Cl3 has three possible structures

1. [Cr(H2O)6]Cl3
2. [Cr(H2O)5Cl]Cl2.H2O
3. [Cr(H2O)4Cl2]Cl.2H2O

[Cr(H2O)3Cl3].3H2O is not a hydrate isomer because here the water molecules are
not attached with any chlorine atom.
(c) Linkage of Salt Isomers :-
• This type of isomerism arises due to presence of ambidentate ligand like NO2-,
CN- and SCN-.

1. [Co(NH3)5NO2]Cl2 and [Co(NH3)5ONO]Cl2

2. In NO2- ligand, The coordinating sites are nitrogen (i.e., NO2- Nitro ligand) or
through oxygen (i.e., ONO Nitrito ligand).
(d) Coordination Isomers :-
• This type of isomerism is exhibited when the complex has two complex ions
in it – ‘Cationic and Anionic’.
• This type of isomerism is caused by the interchange of ligands between the
two complex ions of the same complex.

• Ex. :- (1) [Co(NH3)6][Cr(CN)6] (2) [Co(NH3)6][Cr(C2O4)3]

[Cr(NH3)6][Co(CN)6] [Cr(NH3)6][Co(C2O4)3]
(d) Stereo Isomerism :-

• They have same molecular formula, same constitution, they differ only with
respect to the spatial orientation of ligands in space around the metal ion.
• The two stereo isomers which are possible are – Geometrical and optical.

(1) Geometrical or cis – Trans Isomers

Coordination no. :- 4

Tetrahedral square planner

• 4-Coordinated complex with tetrahedral geometry do not exhibit Cis – Trans
isomerism, because relative position of ligands remain same for each other.

• It is exhibited by 4-coordinated complex with square planar geometry.

• Note:- There are only few possible cases which shows geometrical isomerism
in square planer complex.
• Such as Ma2b2, Ma2bc, Mabcd, M(AB)2.

• G.I. in coordinate no. :- 4 ---> make pair of ligand if two or more than two
different sets are possible then it will show G.I. .
# Geometrical Isomers with Coordinate Number = 4 (Square Planar Complexes)

(1) Complexes with general formula, Ma2b2 (where both a and b are monodentate) can
have Cis-and trans isomers.
(2) Complexes with general formula Ma2bc can have Cis- and trans- isomers.

(3) Complexes with general formula, Mabcd can have three isomers.
(4) [M(AB)2]
M :- central metal atom/ion.
AB :- Bidentate ligand with different donor atoms.

Ex.:- Diglycinato platinum(2)complexes

# Optical isomerism in coordination number (4) :-

(a) Tetrahedral -------> do not show O.I.

(b) Square Planar ------> do not show O.I.

# Geometrical isomerism and optical isomerism with Coordination number (6)
and monodentate ligand.

(a) Make pairs if more than 1 set is farmed it will show G.I.

(b) If in a set one pair both is same like (aa) or (bb) or 2 pairs are same like (ab)(ab) optically
inactive.

(1) [MA6]

(AA)(AA)(AA) -------> No G.I. possible optically inactive.

(2) [MA4B2]

(AA)(AA)(BB) 2 G.I. is possible

(AB)(AB)(AA) Optically inactive
(3) [MA3B2C]

(AA)(AB)(BC)
(AB)(AB)(AC) 3 G.I. possible
(AA)(AC)(BB) Optically inactive

(4) [MA3B3] ------------> facial and meridonial

fac. mer.

(AA)(BB)(AB) 2 G.I. possible

----------->
(AB)(AB)(AB) optically inactive
(5) [MA3BCD]
:- 4 G.I. are possible
(AA)(AB)(CD) -------------------> Optically inactive
(AA)(AC)(BD) --------------------> Optically inactive
(AA)(AD)(BC) -------------------> Optically inactive
(AB)(AC)(AD) -------------------> Optically active

[MA3BCD] ------> Total number of stereoisomers

= (3 G.I. + 0 O.I.) + (1 G.I. + 1 O.A.) = 3+2 = 5
 General formula Total No. of geometrical isomers
Mabcdef 15
Ma2bcde 9
Ma2b2cd 6
Ma2b2c2 5
Ma3bcd 4
Ma3b2c 3
Ma3b3 2
Ma4bc 2
Ma4b2 2
Ma5b Nil
Ma6 Nil
Here M = central atom; a, b, c, d, e, f = Monodentate ligands
# Optical isomers with Coordination number (6) and Bidentate ligand :-

• Check Plane of symmetry :-

(1)If present optically inactive
(2)If absent optically active.

• Or non-super imposable mirror image optically active.

(1) [M(AA)2B2] :-
Total
stereoisomers =
1+2=3
(1) [M(AA)3] :-
Organometallic Compounds :-

Compounds in which C-atom is directly bonded with less electronegative element.

(Ge, Sb, B, Si, P, As) Also form organometallic compounds.

Ex. (a) [ R-Zn-R dialkylzinc (Frankland reagent)

R-Mg-X Alkyl Magnesium halide (Grignards reagent)

(b) These are not organometallic compounds because is these compounds metal is
not directly attached with carbon atom.
(c) Carbides and carbonates are not considered OMC because in these compounds
metal carbon bond has ionic nature.

Classification of Organometallic Compounds :-

OMC can be classified into three
main categories :-

 𝝈-Bonded OMC : These compounds are formed mostly by non transition and
metalloid elements.

Ex. :- R-Mg-X ------> (Grignard’s reagent)

(CH3)2Zn -------> (Dimethyl zinc or Frankland’s reagent)
R2Cd --------> (dialkyl cadmium)
(C2H5)4Pb -------> (Tetra ethyl lead) – used as antiknocking agent in petrol.
𝝅-Bonded OMC : These are usually formed by transition metals.

Ex. :- Ferrocene --------------> [Fe(𝜼5-C2H5)2] where 𝜼 = No. of carbon atoms

combined with metal atom.

Zeise’s salt ---------------> K[PtCl3(𝜼2-C2H4)]

Dibenzene chromium -----------> [Cr(𝜼6-C6H6)2]

 𝝈 and 𝝅-Bonded OMC :- Transition metals of group 6, 7, 8, 9 and 10 in their zero

oxidation state form such type of OMC. The carbonyl compounds of these
metals have both 𝝈 and 𝝅-Bonds.

Ex. :- [Ni(CO)4], [Fe(CO)5],[Mn2(CO)10].

# Crystal Field Theory :-

(a)Ligands are treated as point charges.

(b)When ligands approach central metal atom then they repel each other and as
both have electrons.
(c)In the electric field of these negative charges, the five d orbitals of the metal
atom no longer have exactly same energy.
(d)The extent of splitting of metal d-orbitals depends upon the nature and
number of ligands surrounding it and the charge on the central metal ion.
# Splitting in octahedral complexes:-
• Thus, in octahedral complexes, the five d-orbitals split up into two sets:
One set consisting of two orbitals (𝒅𝒙𝟐 −𝒚𝟐 and 𝒅𝒛𝟐 ) of higher energy (eg orbitals) and the
other set consisting of three orbitals (dxy, dyz, and dzx) of lower energy (t2g orbitals).
# SPLITTING IN TETRAHEDRAL COMPLEX
• Here ligands approach in between the axis dxy , dyz and dxz energy increases due
to more repulsion and energy of 𝒅𝒙𝟐 −𝒚𝟐 and 𝒅𝒛𝟐 decreases.
# SPLITTING IN SQUARE PLANAR COMPLEXES:-
CALCULATION OF CRYSTAL FIELD STABLIZING ENERGY (CFSE)

(1)For octahedral = [-0.4(nt2g) + 0.6(neg) ]∆° + Pairing energy (P.E.)

where nt2g = number of electron in t2g orbitals
neg = number of electron in eg orbitals
∆° = crystal field splitting energy

(2) For tetrahedral = [-0.6(ne) + 0.4(nt2) ]∆° + Pairing energy (P.E.)

where nt2 = number of electron in t2 orbitals
∆° = crystal field splitting energy
# APPLICATION OF CRYSTAL FIELD THEORY
Application of C.F.T are

(1)To predict the geometry that the compound is either inner orbital or outer orbital
complex. d 2sp3 d2sp3

(1)To calculate the magnitude of paramagnetism.

(2)To show the colour property. :- d1 to d9 => d-d transition occur compound coloured.
d0 – d10 => colourless
Factors affecting CFSE :-