TOPIC: Coordination Chemistry

Review of Important Concepts: [Concept Boosters]

1. Molecular / Addition Compound: Molecular / Addition compounds are formed when stoichiometric amounts of two
or more simple compounds join together. Molecular / Addition compounds are of two types.
Double salts: Those which retain their identity in solutions are called double salts. For example.
KCl + MgCl2 + 6H2O KCl.MgCl2. 6H2O
carnallite
K2SO4 + Al2(SO4)3 + 24 H2O K2SO4.Al2(SO4)3.24H2O
potash alum
Complex compounds: Those which loose their identity in solution (complexes). For example.
CuSO4 + 4 NH3 CuSO4.4 NH3 or [ Cu(NH3)4]SO4
tetrammine copper (II) sulphate
Fe(CN2) + 4 KCN Fe (CN2). 4KCN or K4[Fe(CN)6]
potassium ferryocyanide
When crystals of carnallite are dissolved in water, the solution shows properties of K +, Mg2+ and Cl– ions. In a similar way, a
solution of potassium alum shows the properties of K+, Al3+ and SO42– ions. These are both examples of double salts which
exist only in the crystalline state. When the other two examples of coordination or complex compounds are dissolved they do
not form simple ions, Cu2+ / Fe2+ and CN–, but instead their complex ions are formed.

2. Representation of Complex Ion :

[MLx]n±
Where, M = Central Metal atom /ion (usually of d-block)
L = Ligand
x = No. of Ligands
n± = charge on coordination
Outside region apart from coordination sphere is called ionization sphere.
3. Central metal atom/ion : Central metal ion acts as an acceptor (Lewis acid) and has to accommodate electron pairs
donated by the donor atom of the ligand, it must have empty orbitals. This explains why the transition metals having
empty d-orbitals form co-ordination compounds readily. Thus, in complexes [Ni(NH3)6]2+ and [Fe(CN)6]3–, Ni2+
and Fe3+ respectively are the central metal ions.
4. Ligands: Species which are directly linked with the central metal atom/ ion in a complex ion are called Ligands. The
Ligands are attached to the central metal atom /ion through co-ordinate or dative bond.
These may be simple ions such as Br., small molecules such as H2O or NH3, larger molecules such as
H2NCH2 CH2 NH2 or N(CH2 CH2 NH2 )3 or even macromolecules such as proteins.
:

H–N–H H – O: – N: –
: :

:C= :C:
H H
The Ligands are thus Lewis bases and the central metal ions / atoms are Lewis acids.
Ligands can be of following types depending on the number of donor atoms present in them.
(i) Mono / Unidentate Ligands: They have one donor atom, i.e., they can donate only one electron pair to the central
metal atom /ion eg., F–, Cl–, Br–, H2O, NH3, CN–,NO2–, OH–, CO etc.

(ii) Bidentate Ligands Ligands: They have two donor atoms and have the ability to link with the central metal atom
/ion at two positions is called Bidentate ligand e.g.
 H H N N
CH2 – N O– O–
C–C
CH2 – N O O
H H
ethylenediamine (en) oxalate (ox)
1,10-phenanthroline (phen)

H H
N N
CH2 – N O– – C – O–
C–O
–
O
O
glycinate (Gly) 2,2-dipyridine (dipy) carbonate

(iii) Tridentate Ligands: Ligands having three donor atoms are called tridentate ligand.
Examples are
H H
H–N N–H
N N
H2C CH2
N
H2C N CH2
H

diethylene triamine (dien) 2,2'2"-terpyridine (terpy)

(iv) Tetradentate Ligands: These ligands possess four donor atoms. Examples are
H H
N (CH2)2 N
CH2COO
–

(C
2
C)

CH2COO– H
)2
2
(H

N N N
H H
CH2COO– H H

Nitriloacetate Triethylene tetramine (trien)

(v) Pentadentate Ligands: They have five donor atoms. For example, ethylenediamine triacetate ion.

O– – C=O
O

O = C – O– O– – C – CH2

CH2 N (CH2)2 N CH2

H
ethylendiamine triacetate ion

(vi) Hexadentate Ligands: They have six donor atoms. The most important example is ethylenediamine tetraacetate
ion.
N CH2 CH2 N

CH2 CH2
H2C
O=C–O O –C=O
– –

CH2

C – O– O– – C
O O

ethylenediamine tetraacetate (EDTA)

(Vii) Ambidentate ligands : There are cerain ligands which have two or more donor atoms but in forming complexes, only
one donor atom is attached to the metal / ion. Such ligands are called ambidentate ligands. Some examples of such
ligands are
M ← NO2– M ← ONO–
nitrite – N nitrite –O
M ← CN– M ← NC–
cyanide isocyanide
M ← SCN– M ← NCS–
thiocyanide isothiocyanide

(Viii) Ligands having more than two donor atoms are called polydentate or multidentate ligands. Multidentate ligands are
known as a chelating ligands, it results in the formation of a stable cyclic ring thus, the complexes formed are also
called chelates. Chelating ligands are usually organic compounds.
5. Co-ordination sphere The central metal atom and the ligands directly attached to it are collectively termed as the co-
ordination sphere. Co-ordination sphere is written inside square brackets, for examples, [Co(NH3)6]3+. Remember
that the central metal atom and the ligands inside the square brackets, behave as a single entity.

6. Co-ordination number (CN) The co-ordination number (CN) of a metal atom /ion in a complex is the total number
of e– pairs accetpted by central metal atom /ion from ligands through coordinate bond. Some common co-ordination
numbers of metal ions are summarised in the following Table (1) and examples of complexes of various co-ordination
number are given in Table (2).
Metal ion Co-ordinaton number

Ag +
2,4
Cu
+
2,4
Cu
2+
4,6
Au +
2,4
Ca 2+
4,6
Fe
2+
4,6
Fe
3+
6
Co
2+
4,6
Co3+ 6
Ni2+ 4,6
Zn2+ 4
Al
3+
4,6
Sc
3+
6
Cr 3+
6
Pd2+,Pt2+ 4
4+
Pd , Pt
4+
6

Complex Co-ordinaton number

[Ag(NH3)2]+ 2
[HgI3]– 3
PtCl42–, Ni(CO)4 4
Fe(CO)5, [Ni(CN)5]3– 5
[Co(NH3)6]3+, W(CO)6 6
[Mo(CN)7]3– 7
[Mo(CN)8]
4– 8
7. Oxidation number/oxidation state (O.S.) of central metal ion: It is a number (numerical value) which represents
the electric charge on the central metal atom of a complex ion. for example the oxidation number of Fe, CO and Ni in
[Fe(CN)6]4–, [Co(NH3)6]3+ and Ni(CO)4 are +2, +3 and zero, respectively.
8. Effective atomic number -EAN (Sidgwick Theory and EAN Rule) : Total no. of electrons present on central metal
atom /ion. after accepting electron pairs from donar atom of ligands through coordinate bond is called E.A.N. of
central metal atom /ion.

E.A.N = Z – O.S. + 2 × C.N.

Sidgwick also suggested that the metal ion will continue accepting electron pairs till the total number of electrons in
the metal ion and those donated by ligands is equal to that of nearest noble gas. This total number of electrons is called
effective atomic number (EAN) of the metal /ion. This will become clear by taking the example of hexamminecobalt
(III) ion [Co(NH3)6]3+
Atomic number of cobalt = 27
In the present complex, cobalt is present in the oxidation state of +3.
E.A.N. of Co3+ = Z – O.S. + 2 × C.N.
= 27 – 3 + 2 × 6 = 36
In the above example since the number 36 corresponds to the atomic number of krypton, according to Sidgwick, the
complex will be stable. Though EAN rule (which states that those complexes are stable whose EAN is the same as the
atomic number of the next noble gas) is applicable in many metal carbonyl complexes, however there are several
examples in which EAN rule is not obeyed.

9. IUPAC NOMENCLATURE OF COMPLEXES :

The rules for the systematic naming of co-ordination compounds are as follows.

(i) The positive part is named first followed by the negative part, whether it is simple or complex.

(ii) In naming of a complex ion, the ligands are named first in alphabetical order, followed by naming of central metal
atom /ion.

(iii) When there are several monodentate ligands of the same kind, then we normally use the prefixes di, tri tetra, penta and
hexa to show the number of ligands of that type. If ligand’s name already contain any of these prefix , then to avoid
confusion in such cases, bis, tris and tetrakis are used instead of di, tri and tetra and name of the ligand is placed in
parenthesis. For example, bis(ethylene diamine) for two en-ligands.

(iv) Negative ligands have suffix-o, positive ligands have suffix -ium, where as neutral ligands have no specific suffix.
The names of negative ligands ending with -ide are changed to ‘o’. [The 2004 IUPAC draft recommends that anionic
ligands will end with–ido]
For example,
F– fluoro /fluorido H– hydrido HS– mercapto
Cl– chloro /chlorido OH– hydroxo/hydroxido S2– sulphido
Br– bromo / bromido O2– oxo / oxido CN– cyano / Cyanido
I– iodo / iodido O22– peroxo / Peroxido

Ligands ending with -ate/-ite are changed to -ato/-ito. For example, SO42– (sulphato), SO32– (sulphito) etc.
Positive groups end with -ium. For example, NH2 – NH3+ (hydrazinium), NO+ (nitrosonium)
(v) Neutral ligands have No special ending and usually common ligands are provided to neutral ligands except NH3
(ammine) H2O (aqua) CO (carbonyl), NO(Nitrosyl).

(vi) The oxidation state of the central metal ion is shown by Roman numeral in brackets immediately following its name.
(vii) Complex positive ions and neutral molecules have no special ending but complex negative ions end with ate. suffix.
Complex ions

Example Negative complex Positive /neutral complex

Ni nickelate nickel
Pb plumbate lead
Sn stannate tin
Fe ferrate iron

(viii) If the complex compound contains two or more metal atoms, then it is termed as polynuclear Complex compound.
The bridging ligand which link the two metal atoms together are indicated by the prefix –. If there are two or more
bridging groups of the same kind, this is indicated by di– –tri – – and so on. If a bridging group bridges more than
two metal atoms, it is shown as  3,  4,  5 or  6 to indicate how many atoms it is bonded.

(ix) Ambidentate ligands may be attached through different atoms. Thus, M–NO2 is called nitro and M–ONO is called
nitrito. Similarly M–SCN (thiocyanato) or M–NCS (Isothiocyanato). These may be named systematically,
thiocyanato–S and thiocyanate –N respectively to indicate which atom is bonded to the metal. This convention may be
extended to other cases where the mode of linkage is ambiguous.

(x) If any lattice component such as water or solvent of crystallisation are present, these follow their name, and are
preceded by the number of these groups in Arabic numericals. These rules are illustrated by the following examples.
(a) Complex cations IUPAC name
[Co(NH3)6]Cl3 Hexaamminecobalt(III) chloride
[CoCl(NH3)5]2+ Pentaamminechloridocobalt(III) ion
[CoSO4(NH3)4]NO3 Tetraamminesulphatocobalt(III) nitrate
[Co(NO2)3(NH3)3] Triamminetrinitrito-N-cobalt(III)
[CoCl.CN.NO2.(NH3)3] Triammine-chloro-cyano-nitro-N-cobalt(III)
[Zn(NCS)4]2+ Tetrathiocyannato-N-zinc(II) ion.
[Cd(SCN)4]2+ Tetrathiocyanato-S-cadmium(II) ion.

(b) Complex anions

Li[AlH4] Lithium tetrahydridoaluminate(III)

Na[ZnCl4] Sodium tetrachloridozincate(II)
K4[Fe(CN)6] Potassium hexacyanidoferrate(II)
Na2[Fe(CN)5NO] Sodium pentacyanidonitrosyliumferrate(II)
K2[OsCl5N] Potassium pentachloridonitridoosmate(VI)
Na3[Ag(S2O3)2] Sodium bis(thiosulphato)argentate(I)
K2[Cr(CN)2O2(O2)NH3] Potassium amminedicyanidodioxidoperoxidochromate(VI)
(c) Organic groups

[Pt(py)4] [PtCl4] tetrapyridineplatinum(II) tetrachloridoplatinate(II)

[Cr(en)3]Cl3 d or l Tris(ethylenediamine) chromium(III)chloride
[CuCl2(CH3NH2)2] Dichloridodimethylaminecopper(II)
Fe(C5H5)2 Bis(η5 –cyclopentadienyl)iron(II)
[Cr(C6H6)2] Bis(η6-benzene)chromium(0)
(d) Bridging groups

[(NH3)5Co.NH2.Co(NH3)5](NO3)5 μ-amidobis[pentaamminecobalt(III) nitrate

[(CO)3Fe(CO)3Fe(CO)3] Tri-μ-carbonyl-bis [tricarbonyliron(0)]
[Be4O(CH3COO)6] Hexa-μ- acetato(O,O')-μ4-oxidotetraberyllium(II)
(basic baryllium acetate)
(e) Hydrates

AlK(SO4)2. 12H2O Aluminium potassium sulphate 12-water

10. ISOMERISM IN COMPLEXES:

Type of isomerism

Structural isomerism Space / stereo isomerism

–Ionisation isomerism –Geometrical isomerism
–Hydrate isomerism –Optical isomerism
–Linkage isomerism
–Coordination isomerism
–Coordination position isomerism

A. Structural Isomerism
(i) Ionisation Isomerism: This type of isomerism is due to the exchange of groups between the complex ion and ions
outside it. [Co(NH3)5Br]SO4 is red -violet. An aqueous solution of it gives a white precipitate of BaSO4 with BaCl2
solution, thus confirming the presence of free SO42– ions. In contrast [Co(NH3)5SO4]Br is red. A solution of this
complex does not give a positive sulphate test with BaCl2. It does give a creamcoloured precipitate of AgBr with
AgNO3, thus confirming the presence of free Br – ions. Other examples of ionisation isomerism are [Pt(NH3)4Cl2]Br2
and [Pt(NH3)4Br 2]Cl2 and [Co(en)2NO2.Cl]SCN, [Co(en)2NO2.SCN]Cl and [Co(en)2Cl.SCN]NO2.

(ii) Hydrate isomerism: These isomers arise by the exchange of groups in the complex ion with water. Three isomers of
CrCl3.6 H2O are known. From conductivity measurements and quantitative precipitation of the ionised Cl –, they have
been given the following
[Cr(H2O)6]Cl3
[Cr(H2O)5Cl]Cl2.H2O
[Cr(H2O)4Cl2]Cl.2H2O

(iii) Linkage Isomerism: This type of isomersim arises when the ligand attached to the central metal ion of a complex in
different ways. Such ligands are called ambidient ligands. Nitrite ion has electron pairs available for co-ordination
both on N and O atoms. SCN too can be bonded through sulphur (-SCN) thiocyanate or through nitrogen (-NCS)
isothiocyanate.
:

N
: :

:O: O
Examples

(a) [Co(NH3)5 ONO]Cl2 and [Co(NH3)5 NO2] Cl2

pentaamminenitrito-o-cobalt(III) chloride pentaamminenitrito-N-cobalt-(III)-chloride
(red) (yellow)

(b) [Mn(CO5).SCN]+ and [Mn(CO5) (NCS]+

pentacarbonylthiocyanto pentacarbonylthiocyanato
–S-manganese (II) ion –N-manganese (II) ion
(iv) Co-ordination Isomerism: When both the cation and anion are complex ions, then isomerism may be caused by the
interchange of ligands between the anion and cation. For example [Pt(NH3)4] [PtCl4] and [PtCl(NH3)3] [PtCl3(NH3)].
These isomers are called co-ordination isomers.

(v) Co-ordination Position Isomerism: In polynuclear complexes, an interchange of ligands between the metal nuclei
gives rise to co-ordinaton position isomerism, for example.
NH2
(NH3)4.Co Co(NH3)4.Cl2 Cl2
O2

NH2
Cl(NH3)3Co Co(NH3)3Cl Cl2
O2

Co-ordination position isomers

(vi). Polymerisation Isomerism : This is not true type of isomerism because it occurs among compounds having the
same empirical formula, but different molecular formula. Thus, [Pt(NH3)2Cl2],[Pt(NH3)4][PtCl4], [Pt(NH3)4][Pt(NH3)Cl3]2 and
[Pt(NH3)3Cl]2[PtCl4] all have the same empirical formula.

B. Stereo Isomerism:
These are the isomers in which ligands have different spacial arrangements around central metal atom /ion in 3-D space.
(i). Geometrical Isomerism Geometrical isomers are the isomers in which the atoms are joined to one another in the
same way but differ in space because some ligands occupy different relative positions in space.

This type of isomerism arises in heteroleptic complexes due to different possible geometric arrangements of the ligands.
Geometrical isomerism is common among coordination compounds with coordination numbers 4 and 6.

Coordination Number Four :

Tetrahedral Complex : The tetrahedral compounds can not show geometrical isomerism as we all know
that all four positions are equivalent in tetrahedral geometry.
Square Planar Complex : In a square planar complex of formula [Ma2b2] [a and b are unidentate], the two ligands ‘a’ may
be arranged adjacent to each other in a cis isomer, or opposite to each other in a trans isomer as depicted.

Square planar complex of the type Ma2bc (where a,b,c are unidentates) shows two geometrical isomers.
Square planar complex of the type Mabcd (where a,b,c,d are unidentates) shows three geometrical isomers.

Example is [Pt(NH3)BrCl(py)]. Three isomers of the complex [Pt(NH3)(NH2OH)(py)(NO2)]+ have been isolated and
identified.
Square planar complex of the type M(AB)2 (where AB are unsymmetrical bidentates) shows two geometrical isomers.
Example is [Pt(gly)2 ] in which gly is unsymmetrical ligand.

Note : M(AA)2, (where AA are symmetrical Bidentate) does not show geometrical isomerism. e.g., [Cu(en)2 ]2+ [Pt(ox)2] 2- etc.

Coordination Number Six :

Geometrical isomerism is also possible in octahedral complexes.

Number of possible isomers and the spatial arrangements of the ligands around the central metal ion for the specific
complexes are given below.
(I). Complexes containing only unidentate ligands
(i) Ma2b4 2 (aa)(bb)(bb)
(ab)(ab)(bb)
(ii) Ma4bc 2 (aa)(aa)(bc)
(aa)(ab)(ac)
(iii) Ma3b3 - -
Complexes of the formula Ma3b3, where a and b are monodentate ligands, may show two isomeric forms called fac. and
mer.. Facial isomers have three identical ligands on one triangular face where as meridional isomers have three identical
ligands in a plane bisecting the molecule. Similar isomers are possible with some chelating ligands.

The facial (fac) and meridional (mer) isomers of [Co(NH3)3(NO2)3].

Note :- Unsymmetrical bidentate ligands also show fac-mer isomerism.

(iv) Ma3b2c 3 (aa)(ab)(bc)

(aa)(bb)(ac)
(ab)(ab)(ac)
 (v) Ma3bcd 4 (aa)(ab)(cd)
(aa)(ac)(bd)
(aa)(ad)(bc)
(ab)(ac)(ad)

(vi) Ma2b2c2 5 (aa)(bb)(cc)

(aa)(bc)(bc)
(bb)(ac)(ac)
(cc)(ab)(ab)
(ab)(ac)(bc)
(vii) Ma2b2cd 6

(viii) Ma2bcde 9

(ix) Mabcdef 15
([Pt(py)(NH3)(NO2)(Cl)(Br)(I)])
[Note : Ma6 and Ma5b have only one form.]

(II) Compounds containing bidentate ligand and unidentate ligands.

(i) M(AA)a3b . Two geometrical isomers are possible.

(ii) M(AA)a2b2 . Three geometrical isomers are possible.

Note : With [M(AA)b4], only one form is possible. M(AA) abcd have six geometrical isomers.

(iii) M(AA)2a2 . Two geometrical isomers are possible.

Geometrical isomers (cis and trans) of [CoCl2(en)2]

(ii). Optical Isomerism:
A coordination compound which can rotate the plane of polarised light is said to be optically active. When the coordination
compounds have same formula but differ in their ability to rotate directions of the plane of polarised light are said to exhibit
optical isomerism and the molecules are optical isomers.
Optical isomers are mirror images that cannot be superimposed on one another. These are called as enantiomers. The
molecules or ions that cannot be superimposed are called chiral. This is due to the absence of elements of symmetry in the
complex. The two forms are called dextro(d) and laevo(l) depending upon the direction they rotate the plane of polarised light
in a polarimeter (d rotates to the right,l to the left).

Tetrahedral complex :
Optical isomerism is expected in tetrahedral complexes of the type [Mabcd] analogous to tetrahedral carbon atom.

(i). For example [As(III)(CH3)(C2H5)(S)(C5H4COO)]2+ , shows optical isomerism as given below.

Here it may be noted that 4 different groups round the central metal ion are not the only requirement to make the complex to
show mirror-image isomerism. All that is required is that the molecule should be asymmetric (i.e., unsymmetrical), i.e., it
should have no plane of symmetry so that it can exist in two mirror-image forms.

(ii) Tetrahedral complexes of Be, B, Cu(II) and Zn(II) with unsymmetrical bidentate ligands have been resolved into optical
isomers. In order for the complex to be chiral, the chelating ligand must be unsymmetrical (not necessarily asymmetric or
chiral, itself). An example is bis(benzoylacetonato) Be(II) complex, [(C6H5COCHCOCH3)2Be]0 whose mirror-image isomers
are shown in figure.

Here it may be noted from the figure that the complex has no centre or plane of symmetry and the two forms are not super
imposable on each other. This explains the resolution of the complex into d-and l-forms.

Square planar complex:

Square planar complexes are rarely found to show the optical isomerism. The plane formed by the four ligating atoms and the
metal ion is considered to be a mirror plane and thus prevents the possibility of chirality. Although, square planar complexes
seldom show optical isomerism, yet a four –coordinated complex of Pt(II), [Pt(II)(NH2.CH(C6 H5).CH(C6 H5 NH2 ).(NH2CH2
C(CH3 )2NH2)]2+ which has square-planar shape has been resolved into two forms by Mills and Quibell in 1935.
Octahedral complex : Optical isomerism is common in octahedral complexes involving didentate ligands. For example,
[Co(en)3]3+ has d and l forms as given below.

d and l of [Co(en)3] 3+

Cis-isomer of [PtCl2(en) ]2+ show optical isomerism as shown below because of the absence of plane of symmetry as well as
centre of symmetry.

But trans isomer of [PtCl2(en)2]2+ does not show optical isomerism.

cis-[Co(NH3)2 Cl2 (en)]+ can show optical isomerism due to the absence of plane of symmetry (POS) as well as centre of
symmetry(COS).

Detailed Analysis of Optical Isomerism in Octahedral Complexes:-

Octahedral Complexes of the type of [Ma6]n± , [Ma5b]n± are optically inactive and don’t show optical isomerism because of
presence of plane of symmetry (POS).
For example, [Co(NH3)6]3+ and [Co(NH3)5Cl]2+ ion both have plane of symmetry and hence are optically inactive.

Optically inactive optically inactive

(i). [Ma4b2]n± type complexes :- An important example of this type of complexes is [Co(NH3)4Cl2]2+ ion which exists in cis
and trans isomeric forms. Both these forms have a plane of symmetry and therefore are optically inactive. Thus, this type of
complexes does not show optical isomerism.

(ii). [Ma4bc]n± type complexes :- An important example of this type of complexes is [Co(NH3)4 (H2O)Cl]2+ ion. This complex
ion exists in cis- and trans- forms. Both these forms are achiral. Therefore, these forms do not show optical isomerism.

(iii). [Ma3b3]n± type complexes:- An important example of this type of complexes is [Co(NH3)4 Cl3] . This complex exist in
facial ( may be treated as cis) and meridonial (may be treated as trans) forms. Both these forms are achiral and optically
active. Therefore, these forms do not show optical isomerism.

(iv). [Ma2b2c2]n± type complexes:- An important example of this type of complex is [Pt(NH3)2(py)2Cl2]2+. This complex ion
exist in total 5 isomers, out of these only one isomer exists as two optical isomers which is mirror image of each other and are
non-superimposable on each other, as shown below.
Isomers (a) and (b) are the mirror images (i.e enantiomers) of each other and are optically active. Isomers (c), (d), (e) and (f)
are achiral and optically inactive.

(v). [Mabcdef]n± type complexes:- [PtIV (py)(NH3)(NO2)(Cl)(Br)(I)] is the only complex of this type. The possible number of
Geometrical isomers of this complex is 15. Each of these 15 geometrical isomers are chiral and hence is optically active.
Therefore, there are 15 pairs of enantiomers (i.e. total number of optical isomers is 30). The optical isomers of one of the 15
geometrical isomers are shown below.

(vi). [M(AA)3]n± type complexes:- Here, AA is a symmetric Bidentate ligand which may be either a neutral or negative ion.
The example of this type of complexes are : [Co(en)3]3+, [Co(ox)3]3- etc, each of which is chiral. Such complexes can exists in
either of two enantiomeric forms (i.e. either d or l isomers) or a racemic mixture of the two. It is to be noted that an
octahedral complex containing three Chelate rings are always chiral and optically active. Therefore, these complexes are
always existing as pairs of enantiomers. Optical isomers of [Co(en) 3]3+and [Co(ox)3]3- ions are shown below.
(vii). [M(AA)2a2]n± type complexes:- An important example of this type of complexes is [Co(en)2Cl2]+ ion. This complex ion
exists as cis- and trans- isomers , cis- isomers is chiral and optically active. Thus, it exists as d- and l- isomers as shown in
given figure. On the other hand, the trans- isomers is achiral and optically inactive, therefore, this trans- isomers does not
show optical isomerism.

(viii). [M(AA)2ab]n± type complexes:- An important example of this type of complexes are is [Co(en)2(NH3)Cl]2+ ion. This
complex ion exists in cis and trans forms. cis- isomers is chiral and optically active. Therefore, it can be resolved into d- and
l- isomers. The d- and l- isomers are shown. On the other hand, the trans, the trans- isomers is achiral and optically inactive.
Therefore, the trans- isomers can not be resolved into d- and l- isomers.
(ix). [M(AA)a2b2] n± type complexes:- Some examples of this type of complexes are: [Co(en)(NH3)2Cl2]+ ,
[Co(C2O4)(NH3)2(NO2)2]+ , [Co(en)(py)2Cl2]+ etc. These complex ions show geometrical isomerism. The cis- isomers are
chiral and optically active. Therefore, these cis- isomers can be resolved into d- and l- isomers. The optical isomers of
[Co(en)(NH3)2Cl2]+ ion are shown.

(x). [M(AB)3] n± type complexes:- An important example of this type of complexes of this type of complexes is [Co(gly)3].
This complex show geometrical isomerism and exists in fac- and mer- isomeric forms. Both these isomers are chiral and
optically active. Therefore, both these isomers (fac- and mer-) can be resolved into d- and l- isomers. The optical isomers of
[Co(gly)3] are shown.
(xi). [M(AA)2(BB)] n± type complexes:- An important example of this type of complexes is [Co(en)2(ox)]+ ion. This complex
is neither cis- nor trans- but it has an optical isomers as shown below.

(xii). [M(AA)2(AB)] n± type complexes:- This type of complexes do not show geometrical isomerism but these are chiral and
optically active. Therefore, these complexes can exist in d- and l- isomeric forms as shown below.

(Optical isomers of [M(AA)2(AB)] n± type complexes where AA is symmetric Bidentate ligand and AB is unsymmetric
Bidentate ligand)
(xiii). [M(AA)(AB)2] n± type complexes:- This type of complexes show geometrical isomerism and all geometrical isomers
are chiral and optically active. Therefore, all the government isomers can exists in d- and l- forms as shown.
(xiv). Octahedral complexes containing optically active ligands:- An important example of this type of complexes is
[Co(en)(pn)(NO2)2]+ ion. This complex ion exists as two cis- and one trans- isomer, each of the cis- isomers is chiral.
Therefore, the cis-isomers exists in d- and l- isomeric forms. On the other hand, the trans- isomer has plane of symmetry has
and therefore, should be achiral and optically inactive but this isomer has optically active ligand (pn). Thus, it would be
optically active.

(xv). Octahedral complexes containing polydentate ligands such as EDTA4-:- The important complexes of this type of
complexes are : [Ca(EDTA)]2-, [Mg(EDTA)]2-, [Co(EDTA)]- etc. These complexes are neither cis- nor trans- but these are
chiral and optically active. Therefore, they exist as d- and l- isomers. The d- and l- isomers of [Co(EDTA)]- are shown below.
(xvi). Bridged Binuclear Octahedral Complexes (i.e. Polynuclear Complexes) :- Optical Isomerism isn’t limited to
mononuclear complexes. Polynuclear complexes containing bridging ligands can also exists as d- and l- isomers. For
examples, the binuclear Co3+ complex ion shown in figure exists as cis- and trans- isomers. The trans- isomers is achiral and
inactive and thus this isomer is an internally optically compensated i.e. it is meso form.

11. BONDING IN COMPLEXES

1. Werner’s Co-ordination Theory :
Alfred Werner put forward his concept of secondary valency for advancing a correct explanation for the
characteristics of the coordination compounds. The fundamental postulates of Werner’s theory are as follows.
(i) Metal possess two types of valencies, namely, primary (principal or ionisable) valency and secondary (auxillary or
non-ioisable) valency.
In modern terminology, the primary valency corresponds to oxidation number and secondary valency to coordination
number. According to werner primary valencies are shown by dotted lines and secondary valencies by thick lines.
(ii) Every metal cation in complex compound has a fixed number of secondary valencies for example Pt 4+ cation has its
six secondary valency.
(iii) Primary valency is satisfied by negative ions, whereas secondary valency is satisfied either by negative ions or by
neutral molecules.
(iv) Primary valency has non-directional character, where as secondary valency has directional character, therefore a
complex ion has its definite geometry eg. [Co(NH3)6]3+ – octahedron.
(v) It is the directional nature of secondary valency due to which co-ordination compound exhibits the phenomenon of
isomerism.
2. Werner’s Representation of Complexes
Consider the case of CoCl3.xNH3 where primary valency = +3 and seconary valency = 6.
Various structures are summarised in given Table
 Werner complexes Modern formula Ionisation Secondary valency Primary valency
satisfied by staisfied by
(A) CoCl3.6NH3 [Co(NH3)6]Cl3 [Co(NH 3) 6]3+ + 3Cl– six (NH3) three (Cl–)
(B) CoCl3.5NH3 [Co(NH3)5Cl]Cl2 [Co(NH 3) 5Cl] 2++2Cl – five (NH3) three (Cl–)
–
–
and one (Cl ) including one (Cl )
with dual nature
+ – –
(C) CoCl3.4NH3 [Co(NH3)4Cl2]Cl [Co(NH 3) 4Cl 2] +Cl four (NH3) three (Cl )
–
and two (Cl–) including two (Cl )
with dual nature
(D) CoCl3.3NH5 [Co(NH3)3Cl3] [Co(NH 3) 3]Cl 3 three (NH3)
–
and three (Cl )

[Note:- From above table, It is clear that conduction of the complexes will be in the order D < C < B < A. ]
They are represented as

NH3 Cl Cl Cl
NH3 Cl
H3N H3N H3N
NH3 NH3 NH3 NH3
Cl Co Cl Co Cl Co Co
NH3 NH3 NH3 NH3
H3N H3N H3N Cl
NH3 Cl NH3 Cl Cl Cl

(A) (B) (C) (D)

3. Valence Bond Theory :

It was developed by Pauling. The salient features of the theory are summerised below :
(i) Under the influence of a strong field ligands, the electrons of central metal ion can be forced to pair up against the
Hund’s rule of maximum multiplicity.
(ii) Under the influence of weak field ligands, electronic configuration of central metal atom / ion remains same.
(iii) If the complex contains unpaired electrons, it is paramagnetic in nature, whereas if it does not contain unpaired
electrons, then it is diamagnetic in nature and magnetic moment is calculated by spin only formula.
Magneticmoment  n(n  2) BM
where n is the number of unpaired electrons in the metal ion.
Magneticm om ent(Bohr m agnetons
) 0 1.73 2.83 3.87 4.90 5.92
Num ber of unpairedelectrons 0 1 2 3 4 5
(iv) When ligands are arranged in increasing order of their splitting power then an experimentally determind series is
obtained named as spectrochemical series.
(This series has been determined experimentally and not a postulate of VBT, However this is given here so that we
can predict structure, electronic configuration, magnetic properties etc of complexes etc)

I– < Br– < S2– < SCN– < Cl– < NO3– < F– < OH– < EtOH < CH3COO– C2O42– < H2O

Weak field ligands

< EDTA < NH3 py < en < dipy < phen < NO2– CN– < CO

Strong field ligands

(v) The central metal ion has a number of empty orbitals for accommodating electrons donated by the ligands.
The number of empty orbitals is equal to the co-ordination number of the metal ion for a particular complex.
(vi) The atomic orbital (s, p or d) of the metal ion hybridise to form hybrid orbitals with definite directional properties.
These hybrid orbitals now accept e– pairs from ligands to form coordination bonds.
(vii) The d-orbitals involved in the hybridisation may be either inner (n – 1) d orbitals or outer n d-orbitals. The complexes
formed in these two ways are referred to as inner orbital complexes and outer orbial complexes, respectively.\
4. Crystal Field Theory (CFT) :

The drawbacks of VBT of coordination compounds are, to a considerable extent, removed by the Crystal Field Theory.
(i) The crystal field theory (CFT) is an electrostatic model which considers the metal-ligand bond to be ionic arising purely
from electrostatic interaction between the metal ion and the ligand.
(ii) Ligands are treated as point charges in case of anions or dipoles in case of neutral molecules.
(iii) The five d orbitals is an isolated gaseous metal atom/ion have same energy, i.e., they are degenerate. This degeneracy is
maintained if a spherically symmetrical field of negative charges surrounds the metal atom/ion. However, when this negative
field is due to ligands (either anions or the negative ends of dipolar molecules like NH3 and H2O) in a complex, it becomes
asymmetrical and the degeneracy of the d orbitals is lost. It results in splitting of the d orbitals. The pattern of splitting
depends upon the nature of the crystals field.

(a) Crystal field splitting in octahedral coordination entities:

(i) In an octahedral coordination entity with six ligands surrounding the metal atom/ion, there will be repulsion between the
electrons in metal d orbitals and the electrons (or negative charges) of the ligands.

(ii) Such a repulsion is more when the metal d orbital is directed towards the ligand than when it is away from the ligand.
Thus, the dx2 – y2 and dz2 orbitals (axial orbitals) which point towards the axis along the direction of the ligand will
experience more repulsion and will be raised in energy ; and the dxy , dyz and dzx orbitals (non axial orbitals) which are directed
between the axis will be lowered in energy relative to the average energy in the spherical crystal field.

(iii) Thus, the degeneracy of the d orbitals has been removed due to ligand electron-metal electron repulsions in the
octahedral complex to yield three orbitals of lower energy, t2g set and two orbitals of higher energy, eg set.

(iv) This splitting of the degenerate levels due to the presence of ligands in a definite geometry is termed as crystal field
splitting and the energy separation is denoted by  (the subscript o is for octahedral). Thus, the energy of the two eg orbitals
will increase by (3/5) and that of the three t2g will decrease by (2/5) .

Figure showing crystal field splitting in octahedral complex.

The crystal field splitting,  depends upon the fields produced by the ligand and charge on the metal ion. Some ligands are
able to produce strong fields in such a case, the splitting will be large whereas others produce weak fields and consequently
result in small splitting of d orbitals. In general, ligands can be arranged in a series in the orders of increasing field strength as
given below :

I– < Br– < S2– < SCN– < Cl– < NO3– < F– < OH– < EtOH < CH3COO– C2O42– < H2O

Weak field ligands

< EDTA < NH3 py < en < dipy < phen < NO2– CN– < CO

Strong field ligands

[ Note: Halide donors < O donors < N donors < C donors ]
Such a series is termed as spectrochemical series. It is an experimentally determined series based on the absorption of light
by complexes with different ligands. For d4 configuration, the fourth electron will singly occupy eg orbital (according to
Hund’s rule) or will undergo pairing in t2g orbital, which of these possibilities occurs, depends on the relative magnitude of
the crystal field splitting,  and the pairing energy, P (P represents the energy required for electron pairing in a single
orbital).
The two possibilites are :
(i) If < P, the fourth electron enters one of the eg orbitals giving the configuration t32g eg 1 . Ligands for which  P are
known as weak field ligands and form high spin complexes.
(ii) If > P, it becomes more energetically favorable for the fourth electron to occupy a t 2g orbital with configuration t2g 4eg0.
Ligands which produce this effect are known as strong field ligands and form low spin complexes.

CALCULATIONOF CRYSTAL FIELD STABILISATION ENERGY (CFSE):-

Formula : CFSE = [-0.4 (n) t2g + 0.6 (n) eg] 0 + *nP

Where n & n are number of electron(s) in t2g & eg orbitals respectively and 0 crystal field splitting energy for octahedral
complex. *n represents the number of extra electron pairs formed because of the ligands in Comparison to normal degenerate
configuration.
(b) Crystal field splitting in tetrahedral coordination entities :
In tetrahedral coordination entity formation, the d orbital splitting is inverted and is smaller as compared to the octahedral
field splitting. For the same metal, the same ligands and metal-ligand distances, it can be shown that t = (4/9)0. This may
attributes to the following two reasons.

(i) There are only four ligands instead of six, so the ligand field is only two thirds the size ; as the ligand field splitting is also
the two thirds the size and
(ii) the direction of the orbitals does not concide with the direction of the ligands. This reduces the crystal field spliting by
2 2 4
roughly further two third. So t = 3 x 3 = 9 
Consequently, the orbital splitting energies are not sufficiently large for forcing pairing and, therefore, low spin
Configurations are rarely observed. Since t < o crystal field spliting favours the formation of octahedral complexes.

Figure showing crystal field splitting in tetrahedral complex.

(c) Crystal field splitting in square planar coordination entities :

The square planar arrangement of ligands may be considered to be one derived from the octahedral field by removing two
trans-ligands located along the Z-axis. In the process, the eg and t2g sets of orbitals is lifted i.e., these orbitals will no longer be
degenerate.
The four ligands in square planar arrangement around the central metal ion are shown in Fig.As the ligands approach through
the axes, theywould have greatest influence on dx2 . y2 orbital, so the energy of this orbital, will be raised most. The dxy orbital,
lying in the same plane, but between the ligands will also have a greater energy though the effect will be less than that on the
dx2 . y2 orbital. On the other hand, due to absence of ligands along Z-axis, the dz2 orbital becomes stable and has energy lower
than that of dxy orbital. Similarly dyz and dxz becom emore stable. The energy level diagram may be represented as Figure
along with tetrahedral and octahedral fields.
The value of sp has been found larger than o because of the reason that dxz and dyz orbitals interact with only two ligands in
the square planar complexes, while in octahedral complexes the interaction takes place only with four ligands. sp has been
found equal to 1.3o. Thus,
sp = (1 + 2 + 3) > o and sp = 1.3 o

12. Stability of complexes

A co-ordination compound is formed in solution by the stepwise addition of ligands to a metal ion. Thus,
the formation of the complex, MLn (M = central metal cation, L = monodentate ligand and n=co-ordination number of
metal ion) supposed to take place by the following n cosecutive steps.
[ML]
M+L ML; K1 =
[M][L]
[ML2]
M+L ML2; K2 =
[ML][L]
[ML3]
ML2 + L ML3; K3 =
[ML2][L]
……………………………………
……………………………………
MLn–1 + L MLn; Kn =

K1, K2, K3........Kn are called stepwise stability constants. With a few exceptions, the values of successive stability
constants decrease regularly from K1 to Kn. The overall stability constant K is given as

M + nL MLn;

K = K1K2K3....Kn =

The higher the overall stability constant value of the complex, the more stable it is. Alternatively, 1/K values called
instability constant explain the dissociation of the complex into metal ion and ligands in the solution. The value of
the stability constant for some of the complexes are given in Table.
Stability constants of complexes
 Complex Stability constant

[Cu(NH3)4]2+
[Ag(NH3)2]
+

[Co(NH3)6]2+
[Co(NH3)6]+
[AgCl2]
–

[AgBr2]–
[Ag(CN)2]
–

[Cu(CN)4]2–
[Fe(CN)6]3–

13.. Factors affecting stability of complex compounds :

(i) The values of stability constant differ widely depending on the nature of the metal ion and the ligand. In general
higher the charge density on the central ion, the greater the stability of its complexes.

(ii) The more basic a ligands, the greater is the ease with which it can donate its lone pairs of electrons and therefore,
greater is the stability of the complexes formed by it.
eg. The cyano and ammine complexes are far more stable than those formed by halide ions. This is due to the fact that
NH3 and CN– are strong Lewis bases.

(iii) The higher the oxidation state of the metal, the more stable is the complex. The charge density of Co3+ ion is more than
Co2+ ion and thus, [Co(NH3)6]3+ is more stable than [Co(NH3)6]2+ . Similarly, [Fe(CN)6]3– is more stable than
[Fe(CN)6]4–.

(iv) Chelating ligands form more stable complexes as compared to mondentate ligands.

14. Application of complexes

The complexes are of immense importance on account of their applications in various fields. During complex
formation there are drastic changes in the properties of metal atom/ion these changes in properties are made use of in
the application of metal complexes.
(i) The detection and estimation of Ni2+ is based on the formation of a scarlet red complex with dimethyl
glyoxime.
OH O–

CH3 – C = NOH CH3 – C = N N = C – CH3

NH4OH
NiCl2 + 2 Ni + 2NH4Cl + 2H2O
CH3 – C = NOH CH3 – C = N N = C – CH3

O OH

H-bonding
(ii) Fe3+ is detected by formation of a blood red coloured complex with KSCN.
Fe 3   3KSCN  Fe(SCN)3  3K 
blood red colour
or
[ Fe(H2O)5 (SCN)]2 
(iii) Many ligand (organic reagents) are used for the gravimetric estimation of number of metal ions.
 Metal ion to be estimated Cu2+ Ni2+ Fe3+ Al3+ Co2+

Organic reagents used Benzoin Dimethyl 8-hydroxy

oxime glyoxime quinoline

(iv) EDTA is used as a complexing agent in volumeter analysis of metal ions like Ca 2+, Mg2+ and Zn2+.

(iv) The co-ordination compounds of the transition metals exhibit a variety of colours. This property is utilised in
colorimetric analysis for the estimation of many metals.

(v). In Metallurgical process, Silver and gold are extracted by the use of complex formation. Silver ore is treated with
sodium cyanide solution with continuous passing of air through the solution. Silver dissolves as a cyanide complex
and silver is precipitated by the addition of scrap zinc.

Native Gold and Silver also dissolve in NaCN solution in presence of the oxygen (air).
4 Ag + 8 NaCN + O2 + 2H2O 3Na[Ag(CN)2] + 3NaOH
Silver and Gold are precipitated by addition of scrap zinc. Nickel is extracted by converting it into a volatile complex,
nickel carbonyl, by use of carbon monoxide (Mond's process). The complex decomposes on heating again into pure
nickel and carbon monoxide.
heating
Ni + 4CO Ni(CO)4 Ni + 4 CO
(iii) In photography, the image on the negative is fixed by dissolving all the remaining silver bromide with hypo solution in
the form of a soluble complex.
AgBr + 2Na2S2O3 Na3[Ag(S2O3)2] + NaBr
(soluble) (soluble)
(iv) In Electroplating, Metal complexes release metal slowly and give a uniform coating of the metal on the desired object
Cyano complexes of silver, gold copper and other metals are used for the electrodeposition of these metals,

(v) In Biological processes, Metal complexes are of immense importance in biological processes. Haemoglobin, the red
blood pigment, which acts as oxygen carrier to different parts of the body is a complex of iron (II). Vitamin B 12 is a complex
of cobalt metal. The green colouring matter of plants, called chlorophyll, is a complex of magnesium. It acts as a catalyst in
photosynthesis.

15. ORGANOMETALLIC COMPOUNDS

Organometallic compounds are defined as those compounds in which the carbon atoms of organic (usually alkyl or aryl)
groups are directly bonded to metal atoms. The compounds of elements such as boron, phosphorus, silicon, germanium and
antimony with organic groups are also included in organometallics. Many organometallic compounds are important reagents
which are used for the synthesis of organic compounds.
Classification of Organometallic Compounds
Organometallic compounds are classified in three classes.
(i) Sigma bonded organometallic compounds: In these complexes, the metal atom and carbon atom of the ligand are
joined together with a sigma bond, For Examples:
(a) Grignard reagents, R – Mg – X where R is an alkyl or aryl group and X is a halogen.
(b) Zinc compounds of the formula R2Zn such as (C2H5)2Zn. (isolated by Frankland).
Other similar compound are (CH3)4Sn, (C2H5)4Pb, Al2(CH3)6, Al2(C2H5)6, Pb(CH3)4 etc.
 H3C CH3 CH3
Al Al
H3C CH3 CH3
Al2(CH3)6 is a dimeric compound and has a structure similar to diborane, (B 2H6). It is an electron deficient compound
and two methyl groups act as bridges between two aluminium atoms.
(ii) Pi-bonded organometallic compounds : These are the compounds of metals with alkenes, alkynes, benzene and other
ring compounds. In these complexes, the metal and ligand form a bond that involves the p-electrons of the ligand.
Three common examples are Zeise's salt, ferrocene and dibenzene chromium.
These are shown below.
H H
C
C
Cl H H

Pt + Fe Cr
K
Cl Cl
Zeise's Salt

Cr
The number of carbon atoms bonded to the metal in these compounds is indicated by the greek letter (eta) with a
number. The prefixes 2, 5 and 6 indicate that 2, 5 and 6 carbon atoms are the metal in the compound.
(iii) Sigma and Pi bonded organometallic compounds : Metal carbonyl compounds formed between metal and carbon
monoxide, belong to this class. These compounds possess both σ-and π-bonding. Generally oxidation state of metal atoms in
these compounds is zero.
They are of two types.
Monomeric : Thosemetal carbonyls which contain only one metal atom per molecule are called monomeric carbonyls.
For examples :[Ni(CO)4] (sp3, tetrahedral); [Fe(CO)5 ] (dsp3, trigonal bipyramidal); [Cr(CO)6] (d2sp3, octahedral) ;
[V(CO)6] (d2sp3, octahedral, only carbonyl which is paramagnetic having one unpaired electron ; this is least stable among
all the four carbonyls)
CO OC CO CO
Co OC
Fe CO
Cr
Ni
OC CO CO OC CO
CO CO CO
(b) Polymeric : Thosemetal carbonyls which contain two ormore than twometal atoms permolecule and they
have metal-metal bonds are called polymeric carbonyl. For example : Mn 2 (CO)10, Co2(CO)9, etc.

Metal carbonyls are mostly solids at room temperature and atmospheric pressure. Themononuclear carbonyls are volatile
and toxic. With the exception of Fe2(CO)9, carbonyls are soluble in hydrocarbon solvents.
Mononuclear carbonyls are either colourless or light-coloured. Polynuclear carbonyls aremore deeply coloured.
Fe3(CO)12, dodecacarbonyltriiron(o), for example, is a deep grass green solid. Metal carbonyls find use as
industrial catalysts and as precursors in organic synthesis.
The metal.carbon bond in metal carbonyls possess both s and p character. The M.C bond is formed by the donation of lone
pair of electrons on the carbonyl carbon (CO is a weak base) into a vacant orbital of the metal. The M.C bond is formed by
the donation of a pair of electrons from a filled d orbital of metal into the vacant antibonding * orbital of carbon monoxide.
Thus carbon monoxide acts as donor (OCM) and a  acceptor (OCM), with the two interactions creating a synergic
effect which strengthens the bond between.CO and the metal as shown in figure.

(i) As M-Cbonding increases, the C-O bond becomes weaken. The greater the positive charge on the central metal atom,
the less readily the metal can donate electron density into the * orbitals of the carbon monoxide ligands to weaken the C-O
bond.
(ii) In contrast, in the anionic complex (i.e. carbonylate anion) the metal has a greater electron density to be dispersed, with
the result that M-Cbonding is enhanced and the C-O bond is diminished in strength.
For example; in isoelectronic complexes the strength of metal-ligand bond increases and strength of C-O bond
in CO decreases (because bond order decreases) as the negative charge on the complexes increases.
Thus order of CO bond strengths;
(a) [Mn(CO)6]+ > [Cr(CO)6] > [V(CO)6]- > [Ti(CO)6]2- (b) [Ni(CO)4] > [Co(CO)4]. > [Fe(CO)4]2-

16. COLOUR IN COORDINATION COMPOUNDS :

Coordination compounds of transition metals have fascinating colours.According to the crystal field theory the colour is due
to the d-d transition of electron under the influence of ligands.We know that the colour of a substance is due to the absorption
of light at a specific wavelength in the visible part of the electromagnetic spectrum (400 to 700 nm) and transmission or
reflection of the rest of the wavelengths. An object that absorbs all visible light appears black. The mechanism of light
absorption in coordination compounds is that photons of appropriate energy can excite the coordination entity from its
ground state to an excited state. Consider the Ti(III) ion in solution, that is [Ti(H2O)6]3+ . This is a violet colour octahedral
complex, where in the ground state of the complex a single electron is present in t 2g level. The next higher state available for
the transition is the empty eg level. If the light corresponding to the energy of yellow-green is absorbed by the complex, it
would excite the electron from t2g level to eg level. Consequently the complex appears violet in colour. In case of copper (II)
ions in solution, for example, it can be imagined that one of the d-electrons from the t2g set (dxy, dyz, dxz orbitals) gets excited to
the eg set ( x2 y2, z2 d d orbitals). In this case since high energy light is transmitted it means that low energy light (red region)
is absorbed. For copper (II) ions in aqueous solution, the energy gap t is relatively small.
Table below gives the relationship of the wavelength of light absorbed and the colour observed.

[Please Note:-
(a) In absence of ligand, crystal field splitting does not occur and as a consequence the substance appears colourless. For
example ; (i) removal of water from violet coloured complex [Ti(H2O)6 ]Cl3 on heating makes it colourless, (ii) similarly
anhydrous copper sulphate (CuSO4) is white, but hydrated copper sulphate (CuSO4 .5H2O) is blue coloured.
(b) The nature of the ligand and the molar ratio of metal : ligands also influence the colour of the complex. For
example ; in the pale green complex of [Ni(H2O)6 ]2+ , the colour change is observed when ethylenediamine is
progressively added to it.]
[[ Most Important Points:-
(i) CH3B(OCH3) is an organometallic compound but B(OCH3) is not.
(ii) The closed ring complexes formed by polydenatate ligands are called Chelates. Chelation leads to stability.
(iii) Estimation of nickel (II) is done by complexing with dimethyl glyoxime (DMG) whereas that of Ca+2 and Mg2+ ions
is done by titrating against EDTA.

(iv) Complex in which ligands can be substituted by other ligands are called labile complexes. For example [Cu(NH3)4]2+
is a labile complex because NH3 ligands can be substituted by CN– ligands.
[Cu(NH3)4]2+ + 4 CN– [Cu(CN)4]2 + 4NH3
(less stable) (more stable)
(v) Another type of geometrical isomerism is also shown by octahedral complexes of the type Ma 3b3.
if each trio of donor atoms occupy adjacent positions at the corner of an octahedral face, then it is called facial (fac)
isomer and when the position are around the meridian of the octahedron, then it is called meridional (mer) isomer.
a b
b a b a
M M
b a a
a
b b
fac-form Mer-form

(vi) Haemoglobin is a complex of Fe, chlorophyll is a complex of Mg, vitamin B12 is a complex of Co.
(vii) s-bond organometallic compounds generally contains a non-transition metal linked to carbon atom of alkyl group by s
bond. For example eg. R-MgX.
(viii) p-bonded organometallics are formed by donation of p-electrons of double bond to the metal atom. For example
Zeise's salt K[PtCl32 C2H4] and Ferrocene Fe(5-C5H5)2
(ix) Grignard's reagent is one of the most useful organometallic compounds. Due to the high polarity of (Cd–Mgd+) bond,
it can be used to synthesise many organic compounds. ]]