Coordinate Compounds ….. By….. G. H.

Reshi

Coordination Chemistry
Class-12th

Coordination
Compounds

Gh. Hassan Reshi

Reseah Officer
State Intute Of Education Kashmir

State Institute of Education Kashmir, 0

Bemina Bypass, Srinagar
State Institute of Education, Kashmir

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 Coordinate Compounds ….. By….. G. H. Reshi
Coordination Compounds

Introduction
Coordination chemistry is the branch of chemistry, which distinctivelydeals with the study of
coordination compounds for their chemical, structural, magnetic and spectral properties.
Coordination compounds are a special class of compounds that consist of a central metal atom
or Metal ion which is surrounded by oppositely charged ions or neutral molecules in more than
its normal valence. They are also called complex compounds or simply complexes. There exist a
large number of biologically important coordination compounds having complex organic
species bound to a central metal ion. For example,
1. Chlorophyll, a green pigment vital for photosynthesis, is a coordination complex of
magnesium.
2. Haemoglobin, an important metalloprotein, is a coordination complex of iron.
3. Vitamin B12, a coordination complex, where central metal is cobalt.
The use of coordination compounds extends to analytical chemistry, metal extraction and
catalysis. Such compounds also find application in medicinal chemistry.

Salt:-It is an ionic compound, which contains cation other than H+ and anion other OH-. It is
formed when an acid combines with a base.

e.g., NaCl, KCl, MgSO4, AlCl3, KNO3, etc.

Double salt:-It is defined as the salt, which contains more than one type of cations.
e.g.,
Potash alum: K2SO4Al2(SO4)3.24H2O
Mohr’s salt: FeSO4(NH4)SO4.6H2O
Carnalite: KCl.MgCl2.6H2O

Both the simple and double salts exist only in solid state and dissociate into their constituent
ions in the solution phase.

Coordination compound:-It is an inorganic salt, which retains its identity in the solid state as
well as when dissolved in water or any other solvent. Such compounds are usually formed by
transition metals or d-block elements. These compounds are also called as coordination
complexes.
e.g.,
K2[PtCl6], [Co(NH3)6]Cl3, K4[Fe(CN)6], [Pt(NH3)2Cl2], etc.

Both double salts as well as coordination compounds are formed by the combination two or
more than two compounds in definite stoichiometric ratio.
e.g.,

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Important terms pertaining to coordination compounds:

1. Coordination entity:It is the central metal atom or ion which is bonded to a definite number
of ions, atoms or molecules. It is that part of the coordination compound which remains as a
single entity, i.e., it does not loose its identity in a solution phase. This part is written in square
brackets and is non-ionizable. It is also called as coordination sphere. For example, in
[Co(NH3)6]Cl3, a coordination entity consists of Co3+ ion bonded to six ammonia molecules.

2. Central metal atom/ion:It is the central metal atom/cation that is surrounded and
coordinately bonded to one or more anions or neutral molecules in a definite geometrical
arrangement. For example, in [Co(NH3)6]Cl3, Co3+ represents the central metal cation and is
being coordinately bonded to six neutral NH3molecules. The central metal ion is also referred to
as Lewis acid.

3. Ligands: The molecules, atoms or ions that surround the metal ion in a coordination
entityare called ligands. The formation of coordinate covalent bonds between ligands and a
metal can bethought of as a Lewis acid-base reaction, where ligands act as Lewis bases. To be a
ligand, a molecule, atom or ion musthave at least one unshared pair of valence electrons, as
illustratedby these examples:

4. Coordination number: It is the total number of ligands which are coordinately bonded to
the central metal atom or ion in a coordination sphere of the coordination compound. For
example, in [Co(NH3)6]Cl3, the coordination number of Co3+ is 6. The most common
coordination numbers are 4 and 6,although coordination numbers of 2 and 5 are also known.
5. Ionization sphere: It represents the counter ion part of the coordination sphere,which may
be an anion or a cation. These anions or cations are written outside the square brackets, and
are ionizable in solution phase.For example,in [Co(NH3)6]Cl3, the three Cl- ions indicate the
ionization sphere.
6. Donor atom: The coordinating atom of the ligand, which is actually donating an electron
pair to the central metal atom or ion is called a donor atom. For example, in the case of neutral
ligands H2O and NH3, oxygen and nitrogen are donor atoms.

7. Oxidation number of central metal: When all the ligands attached to the central metal are
removed, the charge that the central metal atom would carry is called its oxidation number. For
example,the oxidation number of cobalt in [Co(NH3)6]Cl3 is +3. It is represented in Roman

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 Coordinate Compounds ….. By….. G. H. Reshi
numeral in parenthesis after the name of the central metal atom. For example, for the above
mentioned complex, it is written as Co(III).
The oxidation state of a transition metal in a complex ion is determined usingthe known
charges of the ligands and the known overall charge of the complexion. In the complex ion
[PtCl6]2−, for example, each chloride ion ligand has anoxidation number of −1. For the overall
charge of the ion to be −2, the Pt musthave an oxida on number of +4.
8. Homoleptic and heteroleptic complexes: When the central metal atom or ion is bonded to
only one type of donor groups, the complex is said to be homoleptic; for example,
[Co(NH3)6]3+.The complex in which the metal atom or ion is bonded to more than one type of
donor groups is called heteroleptic complex; for example, [Co(NH3)4Cl2]1+.

Classification of ligands
Ligands are classified many ways according to theircharge, size, type of the coordinating
atom(s) and the number of electrons donated to the central metal.
On the basis of their charge, the ligands can be categorized into the following types.
(A) Neutral ligands
Such ligands possess no net charge and are coordinated to the metal atom or ion through a
lone pair of electrons.

(B) Negatively charged ligands

These ligands possess a net negative charge.

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(C) Positively charged ligands

These ligands have a net positive charge.

Ligands have also been classified on the basis of their denticity. Denticity refers to the number
of times a ligand bonds to a central metal atom or ion through non-contiguous donor sites. There are
many ligands capable of binding metal ion via multiple sites since the ligands can have lone pair of
electrons or charges on more than one atom. Accordingly, the ligands can be of following types.

1. Unidentate ligands:Ligands which can coordinate to the central metal atom or ion via only
one donor atom (i.e., their denticity is one) are known as unidentate or monodentate ligands.
e.g., H2O, NH3, PH3, PPh3, OH-, Cl-, NH2-, NO+, Pyridine, etc.

2. Bidentate ligands: These ligands are capable of binding to the central metal ion via two
binding sites (i.e., their denticity is two). e.g.,

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 Coordinate Compounds ….. By….. G. H. Reshi

4. Tridentate ligands: These ligands possess three donor sites or their denticity is three.
e.g.,

5. Tetradentate ligands: Ligands which can bind to the central metal ion through four
donor sites (denticity is four) are called tetradentate ligands.
e.g.,

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6. Pentadentate ligands: Ligands which can coordinate to the central metal ion through five
donor sites (denticity is five) are called pentadentate ligands.
e.g.,

6. Hexadentate ligands: Ligands which can coordinate to the central metal ion via six donor
atoms (denticity is six) are called hexadentate ligands.
e.g.,

In general, ligands having more than two donor atoms are called as polydentate ligands.

Other types of ligands:

1. Flexidentate ligands: The ligands which show variable denticity are called as flexidentate
ligands. When these ligands get coordinated to the metal atom or ion, they give rise to the
formation of two types of complexes. In one they get linked to the metal center via one donor
atom only while in the formation of the another type of the complex, they get coordinated to
the metal center through both of its donor atoms.
e.g., SO42-, CO32-, EDTA4-, NO3-, etc

2. Chelating ligands: The ligands which form the ring structures with the central metal atom or
ion are called as chelating ligands. All di- and polydentate ligands can act as chelating ligands.

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 Coordinate Compounds ….. By….. G. H. Reshi
The complex formed by the chelating ligands is called as the chelating complex or
simply chelate (derived from a Greek word chele meaning claw).

Chelating ligands form more stable complexes than the similar complexes in which such
ligands act as monodentate ligands. This is called as chelation or chelate effect.

3. Ambidentate ligands: Ligands containing more than one coordinating atoms, but get linked
to the central metal atom or ion through only one donor atom at a time are called as
ambidentate ligands.
e.g., SCN-, CN-, NO2-
O

M S C N M N
thiocyanato O
nitrito-N

M N C S M O N O
isothiocyanato nitrito-O

4. Bridging ligands: Unidentate ligands which can act as bidentate ligands when they are
attached to the two metal atoms or ions at the same time are called as bridging ligands. A
bridging ligand must have at least two unshared pair of electrons.Such ligands result in the
formation of bridged or polynuclear complexes.
e.g., N2, OH-, X- (Cl-, Br-, I-), O2-, NH2-NH2, SO42-, NO2-, etc.

Nomenclature of Coordination Compounds

The general rules for naming the coordination compounds and writing their formulae
have been set by IUPAC to avoid any ambiguity.

Rules for Formula of the Coordination Compounds

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1. The central atom is written first followed by the ligands.
2. The ligands are listed in the alphabetical order according to theirsymbol of formulae.
3. The polyatomic ligands are shown in parentheses.
e.g., triamminechloridocyanonitrocobalt(III) [Co(NH3)3ClCN(NO2)]
4. The complex organic ligands are written in the abbreviated forms inparentheses.
5. The coordination sphere is enclosed in a square bracket.
6. The charge on the complex species, if present, is written outside thesquare bracket as a
superscript.For example, hexaaquairon(II)ion [Fe(H2O)6]2+.

Naming of Coordination Compounds

1. The cation is named before the anion, as in other ionic compounds. The ruleholds
regardless of whether the complex ion bears a net positive or a net negativecharge. In the
compounds K2[Fe(CN)6] and [Co(NH3)4]Cl, for example, we namethe K+ and
[Co(NH3)4]+cations first, respectively.
2. Within a complex ion, the ligands are named first, in alphabetical order, and themetal ion
isnamed last.There should be no space between the name ofthe ligand and the name of the
central metal ion.
3. The names of negative ligands end with ‘o’, names of positive ligandsend with ‘ium’and the
names of neutral ligands are written as such. The exceptions are H2O (aqua),CO (carbonyl),
and NH3 (ammine). The anionic organic ligands where carbon acts as a donor atom ‘o’; e.g.,
CH3- is named as methyl (not methylo).Table 9.1 lists some common ligands andtheir
nomenclature.

Table 9.1. Names of Some Common Ligands in Coordination Compounds

Anionic ligand Name in complex Neutral ligand Name in complex
-
Cl Chlorido NH3 Ammine
-
Br Bromido H2O Aqua
2-
O Oxo NO Nitrosyl
OH- Hydroxo CO Carbonyl
CN- Cyano N2 Dinitrogen
2-
C2O4 Oxalato O2 Dioxygen
2-
CO3 Carbonato C5H5N Pyridine
-
CH3COO Acetato H2N-NH2 Ethylenediamine
NO2- Nitro PPh3 Triphenylephosphine
-
ONO Nitrito or Nitro-O

4. When two or more of the same ligand are present, use nummerical prefixes di, tri,tetra,
penta, and hexa, to specify their number. Thus, the ligands in the cation[Co(NH3)4Cl2]+ are
“tetraamminedichloro.”However, for ligands alreadyhaving a prefix like di, tri, etc., prefixes
bis, tris, tetrakis, etc.are used. In such cases, the name of the ligands is written in brackets;
e.g., (en)2 is written as bis(ethylenediammine)(Note that prefixes are not used forthe
purpose of alphabetizing the ligands.)
5. The oxidation number of the metal is indicated in Roman numerals immediatelyfollowing
the name of the metal. For example, the Roman numeral III is used toindicate the +3
oxidation state of chromium in [Cr(NH3)4Cl2]+, which is

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 Coordinate Compounds ….. By….. G. H. Reshi
calledtetraamminedichlorochromium(III) ion. (Note that no space is provided between
thename of the metal and the parentheses.)
6. If the complex is an anion, its name ends in -ate. In K4[Fe(CN)6], for example, theanion
[Fe(CN)6]4− is called hexacyanoferrate(II) ion. Note that the Roman numeralindicating the
oxidation state of the metal followsthe suffix -ate. Table 22.5 liststhe names of anions
containing metal atoms.
7. A bridging ligand is indicated by the word µ(mu), before the name of such ligand, separated
from the rest of the complex by a hyphen(−).
8. If the same ligand is present as a bridging and as a non-bridging ligand,the bridging ligand is
named first.
9. For ambidentate ligands, the point of attachment is indicated bymentioning the symbol of
the atom in parenthesis after the name ofligand.
11. Water of crystallization, if any, is named as,
[Cr(NH3)6]Cl3•2H2OHexaamminechromium(III)chloride-2-water or -dihydrate
12. Geometrical isomers are designated by the term cisor trans.
13. Optical isomers are designated by the symbol (+) or d and (−) or l toindicate dextrorotatory
and laevorotatory respectively.
14. Abbreviations are used for complex ligands.
15. The suffix ion is added with a name of the complex ion.

Table 9.2.Examples of the coordination complexes

Formula of the complex Name of the coordination complex
[Cr(NH3)3(H2O)3]Cl3 triamminetriaquachromium(III) chloride
K2[Zn(OH)4] potassium tetrahydroxidozincate(II)
K3[Al(C2O4)3] potassium trioxalatoaluminate(III)
[Ni(CO)4] tetracarbonylnickel(0)
[CoCl2(en)2]+ dichloridobis(ethane-1,2-iamine)cobalt(III)
[Pt(NH3)2Cl(NO2)] diamminechloridonitrito-N-platinum(II)
K3[Cr(C2O4)3] potassium trioxalatochromate(III)
Hg[Co(SCN)4] mercury tetrathiocyanatocobaltate(III)
K3[Fe(CN)6] potassium hexacyanoferrate(III)
[Co(H2NCH2CH2NH2)3](SO4)3 tris(ethane-1,2–diammine)cobalt(III) sulphate

Structure of Coordination Compounds

The geometry of a coordination compound often plays a significant role in determining

its properties. Figure 9.1 shows four different geometric arrangements for metalatoms with
monodentate ligands. In these diagrams, we see that structure and thecoordination number of
the metal relate to each other as follows:

Coordination number Structure

2 Linear
4 Tetrahedral or square planar
6 Octahedral

SomeCommon geometries of complex

ions. In each case M is a metal and L is a
monodentate ligand.

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Isomerism in Coordination Compounds

The coordination compounds which have the same molecular formula but different
structural arrangements or binding of the surrounding ligandsaround the central metal atom
or ion exist as isomers. These isomers have different physical and chemical properties.
Following two main types of isomerism are exhibited by coordination compounds:

(A). Structural Isomerism: This type of isomerism arises due to the difference in the binding of
ligands with the central metal atom or ion.

(B). Stereoisomerism: This type of isomerism is shown by complexes in which the ligand
atoms differ in their locations in space. As a result, their physical and chemical properties
differ.

Structural isomerism is one of thefollowing types:

1. Ionisation Isomerism: This type of isomerism arises due to difference in the position of
ions within or outside the coordination sphere. As a result, different ions are produced on
dissolving such isomers in solution.
For example, Co(NH3)5BrSO4 exists in two ionisation isomers.

Similarly, [CoCl2(NH3)4]NO2 and [CoClNO2(NH3)4]Clareionisation isomers.

2. Hydrate Isomerism:This type of isomerism arises due to difference in the position of water
of hydration within or outside the coordination sphere. For example, three hydrate isomers of
CrCl3•6H2O are [Cr(H2O)6]Cl3, [CrCl(H2O)5]Cl2•H2O and [CrCl2(H2O)4]Cl•2H2O.

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 Coordinate Compounds ….. By….. G. H. Reshi
AgNO3 Conc. H2SO4
3AgCl [Co(H2O)6]Cl3 No loss of water
Hexaaquachromium(III) chloride
(Violet)
AgNO3 Conc. H2SO4
2AgCl [Co(H2O)5Cl]Cl2 H2O Loses one H2O
Pentaaquachlorochromium(III) chloride
monohydrate
(Green)
AgNO3 Conc. H2SO4
AgCl [Co(H2O)4Cl2]Cl 2H2O Loses two H2O
Tetraaquadichlorochromium(III) chloride
dihydrate
(Green)
Similarly, Co(en)2Cl3•H2O exists as two hydration isomers, i.e., [CoCl(en)2(H2O)]Cl2 and
[CoCl2(en)2]Cl•H2O.

3. Linkage Isomerism: This type of isomerism is shown by compounds having ambidentate

ligands. For example, the SCN− ion may bind with the central metal ion either through N- or
through S-atom as found in [Pd(en)(SCN)2] and [Pd(en)(NCS)2]. Similarly, [Co(NO2)(NH3)5]Cl2 and
[Co(ONO)(NH3)5]Cl2 are linkage isomers.
4. Coordination Isomers: This type of isomerism is shown by compounds having both cationic
and anionic complexes. There can be an exchange of ligands between the two complexes giving
rise to coordination isomers.
For example,[Cu(NH3)4][PtCl4] and [Pt(NH3)4][CuCl4]
[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
5. Coordination Position Isomerism: This type of isomerism is shown by polynuclear complexes
in which there is exchange of ligands between the linked metal ions. For example,

Stereoisomerism or Space isomerism is of two types, i.e.,geometrical and optical

isomerism.
1. Geometrical Isomerism: This type of isomerism arises due to difference in position of
ligands around the central ion, i.e. ligands may occupy adjacent positions or opposite
positions to one another and are referred as cis-trans isomers respectively. Hence, this
isomerism is also known as cis-trans isomerism.
Compexes with coordination numbers (CN) 2 and 3 and complexes withtetrahedral
geometry do not show this type of isomerism as all the positionsare adjacent to one
another in these cases. Most important is the case ofcomplexes with square planar
geometry (CN = 4) and octahedral geometry(CN = 6).
(a) Square Planar Complexes:These complexes can be of eight types:Ma4, Ma3b, Mab3,
Ma2b2, Ma2bc, M(ab)2,Mabcd and M2a2b4. Out of these, every spatial arrangement ofligands
around the metal ion is equivalent in case of Ma4, Ma3band Mab3. Other cases are discussed
below:

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(i) Ma2b2typecomplexes: In cis-form, two ‘a’ groups are adjacent to oneanother and in
trans-form, ‘a’ and ‘b’ groups are adjacent to oneanother.For example, [PtCl2(NH3)2],
[PtCl2(py)2] and[Pd(NO2)2(NH3)2].

(ii) Ma2bctypecomplexes: Incis-form, two ‘a’ groups are adjacent and in trans-form,
opposite toone another.For example, [PtCl(NH3)(Py)2].

py py

Cl Cl

Pt Pt

py H3N

NH3 py
Cis Trans
(iii) Mabcdtype complexes:In this, the position of one ligand isfixed and other ligands are
put trans to it.For example, three isomeric forms have been reported for
[Pt(NO2)(Py)(NH3)NH2OH], [Pt(NH3)(Py)(Cl)(Br)] and [Pt(C2H4)(NH3)(Cl)(Br)].

(iv) M(AB)2 type complexeswith unsymmetrical bidentate chelating ligands (AB). For
example, in [Pt(gly)2], gly is anunsymmetrical bidentate chelating ligand. It shows cis-
transisomerism as,

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 Coordinate Compounds ….. By….. G. H. Reshi
(v) [M2a2b4 type complexeswith bridged binuclear forms. Forexample, Pt2(Et3P)2Cl4] has
been found to show cis-transisomerism as,

(b) Octahedral Complexes:Out of the possible types, only Ma6 andMa5b do not show
geometrical isomerism. In octahedral complexes, positions can be numbered as,

(i) Ma4b2 type complexes: In cis-form, two ‘b’ groups have adjacentpositions(1, 2) and in
trans-form, two ‘b’ groups are diagonally opposite toeach other (1, 6). For example,
[CrCl2(NH3)4]+ and [CoCl2(NH3)4]+.
Cl Cl

H3N Cl H3N NH3

Co Co

H3N NH3 H3N NH3

NH3 Cl
Cis-isomer (1,2-isomer) Trans-isomer (1,6-isomer)

(ii) Ma3b3 type complexes:In cis-isomer, three ‘a’ groups are adjacent at 1,2 and 3 positions
and in trans-isomer these occupy 1, 2 and 6positions. Since in cis-isomer, the three same
ligands are on onetriangular face, so it is also called asfacial isomer or 1, 2, 3-
isomer;whereas in trans-isomer, the three same ligands are in a planebisecting the
molecule, so it is called as meridionalor 1, 2, 6-isomer.For example, [Co(NH3)3Cl3] exists
infac and mer forms.

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(iii) Ma2(AA)2type complexeswith symmetrical bidentatechelating ligand (AA). For example,

[Co(en)2Cl2]+,etc. Here, the position of chelating ligand decides the type ofisomer.

(iv)[Mabcdef] type complexes:Only one such compound [Pt(py)(NH3)(NO2)ClBrI] has been

obtained in three different forms, although15 different geometrical isomers are possible.
These isomers may be written by fixing a ligand at one position and then placing other
ligands trans to it.

2. Optical Isomerism: There are certain compounds which have the ability of rotating the
plane of polarized light. The compounds are said to be optically active and the phenomenon
is called as optical isomerism. The isomers which rotate the plane of polarized light equally,
but in opposite direction are called as enantiomers or enantimorphs. The isomers that
rotate the plane of light to the right are called dextrorotatory (d or +) complexes while as
those which rotate it to the left are laevorotatory (l or -) complexes. Thus, in an equimolar
mixture of two enantiomers, called a racemic mixture, the net rotation is
zero.Enantiomersare nonsuperimposable mirror images. (Superimposable means that if one
structure is laid over the other, the positions of all the atoms will match.) Like geometric
isomers, optical isomers come in pairs. However, the optical isomers of a compound have
identical physical and chemical properties, such as melting point, boiling point, dipole
moment, and chemical reactivity toward molecules that are not themselves optical isomers.

Optical isomers are described as chiral (from the Greek word Mirror image of
left hand

for “hand”) because,like your left and right hands, chiral molecules Left hand

are nonsuperimposable.The structural relationship between two Mirror

optical isomers is analogous to therelationship between your left

and right hands. If you place your left hand in front ofa mirror, the
image you see will look like your right hand. Your lefthand and
right hand are mirror images of each other. They are

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 Coordinate Compounds ….. By….. G. H. Reshi
nonsuperimposable,however, because when you place your left hand over your right hand
(with bothpalms facing down), they do not match. This is why a right-handed glove will not
fitcomfortably on your left hand.Isomers thatare superimposable with their mirror images
are said to be achiral.
Some examples of optical isomerism in coordination complexes are discussed as follows:

(a) Complexes with Coordination Number 4:One tetrahedral complex

bis(benzoylacetonato)beryllium(II) has been shown to be optically active.
Similarly, one square planar complex of Pt(II), iso-butylenediaminemeso-
stilbenediamineplatinum(II)cation, has been found to be opticallyactive.

(b) Complexes with Coordination Number 6:Octahedral complexes of the M(AA)2, where
(AA) is a symmetrical bidentate ligand like ethylenediamine, show optical isomerism. For
example, [Co(en)3]3+ and [Cr(ox)3]3-.

Octahedral complexes of the M(AA)2a2 and M(AA)2ab, where (AA) is again a symmetrical
bidentate ligand like ethylenediamine, show optical isomerism. Examples are [Co(en)2Cl2]+,
[Rh(en)2Cl2]+, etc. These complexes exist as cis and trans isomers, and trans-isomer has a
superimposable mirror image and is optically inactive.

The cis-isomer exists as non-superimposable images and is thus optically active.

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Complexes of the type [M(AA)a2b2] having only one symmetrical bidentate ligand also display optical
isomerism. Example of this type is[CoCl2(en)(NH3)2].

Bonding in Coordination Compounds

Coordination compounds have been in use since ancient times but were acomplete
mystery without any knowledge of their structure or bonding. Various theories have been
put forward to account for the structure and bonding of thecoordination compounds from
time to time.These include Werner’s Coordination Theory, Valence Bond Theory (VBT),
Crystal Field Theory (CFT), Ligand Field Theory (LFT) and Molecular Orbital Theory (MOT).
Some of these theories are discussed herein

Werner’s Theory of Coordination Compounds

The first fruitful attempt on physical, chemical, structural and behavioural aspects of
coordination compounds was done by Swiss chemist, Alfred Werner (1866-1919). He
proposed his theory for coordination compounds in 1893, and after work of 20 years won
the Nobel Prize for Chemistry in 1913. This theorywas based on simple reaction chemistry.
The main postulates of this theoryare:

1. In a coordination compound, a metal atom exhibits two types ofvalencies, i.e. primary
valency and secondary valency.

2. Primary valency is non-directionable and ionizable. According tomodern explanation,

primary valency corresponds to the oxidationstate of the metal ion whereas the secondary
valency is directional andnon-ionizable. In modern explanation, it corresponds to
thecoordination number of the metal ion.

3. Every metal atom tends to satisfy both types of valencies. Primaryvalencies can be
satisfied only by the negative ions but the secondaryvalencies can be satisfied either by the

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negative ions or by the neutralmolecules. A negative ion may satisfy both the valencies in
somecases.

4. The primary valencies are shown by dotted lines while the secondaryvalencies are
shown by thick lines. Since the secondary valencies aredirectional, they lead to a definite
geometry of the compound. Wernerstudied the action of silver nitrate on cold solutions of a
series ofcoordination complexes, which can besummarised below:

(a) In case of CoCl3.6NH3, the stoichiometry of complex andprecipitates of AgCl formed was
in the ratio 1:3.Werner deducedthat three chloride ions were ionizable and form the
primaryvalency, while the six ammonia ligands form the secondaryvalency. The complex can
be written as [Co(NH3)6]Cl3, in modernterminology.

(b) In case of CoCl3.5NH3, Werner found that the stoichiometric ratioof the complex and
precipitates of AgClwas 1:2. He deduced that inthis complex, one Cl- ion is acting as both
primary and secondaryvalencies, while the two Cl- ions are being ionizable andhence, serve
only as primary valency. The five NH3 ligands serveas secondary valency. In the modern
system, the complex can bewritten as [Co(NH3)5Cl]Cl2.

(c) In case of CoCl3.4NH3, the stoichiometric ratio of the complex andAgCl was 1:1,
indicating only one Cl- ion as primary valency, while theother two Cl- ions serve for both
primary and secondary valencies.The complex can be written as [Co(NH3)4Cl2]Cl.

(c) In case of CoCl3.3NH3, all the three Cl- ions are satisfying both the primary as well as
secondary valencies, so none of the Cl- ions can be precipitated out as AgCl.

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Thus, Werner was able to conclude that in all these complexes, thenumber of secondary valencies
was six, i.e., six coordinate bonds are formedby the central metal ion with its ligands.

Limitations of Werner’s Theory of Coordination Compounds

1. It could not explain why some elements have higher tendency to form coordination
compounds while as certain elements have the least tendency to form such compounds.
2. It could not explain the directional nature of secondary valencies.
3. It could not explain the magnetic and optical properties of the coordination compounds.

Valence Bond Theory (VBT) of Coordination Compounds

This theory was developed by Linus Pauling in 1931, and gave the valence bond
treatment of bonding to coordination complexes. The main postulates of this theory are:

1. The metal-ligand bond arises by the donation of pairs of electrons by ligands to the
metal atom or ion.
2. The central metal atom or ion under the influence of ligands makes available a number
of empty orbitals.
3. The number of such empty orbitals is equal to the coordination number of the metal
atom or ion.
4. Ligand should possess at least one filled orbital containing a lone pair of electrons for
the formation of a coordinate bond with the metal center.
5. The atomic orbitals (n-1)d, ns, np, or ns, np, nd orbitals made available by the central
metal atom or ion, being different in energies, shapes and orientations, undergo
hybridization to yield a set of equivalent orbitals (hybrid orbitals) of definite geometry
such as octahedral, tetrahedral, square planar and so on.
6. The vacant hybrid orbital of the metal center undergoes overlap with the filled ligand
orbital to form a metal-ligand coordinate covalent bond. These bonds are of equal
strength and directional in nature.

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 Coordinate Compounds ….. By….. G. H. Reshi
7. Octahedral, square planar and tetrahedral complexes are formed as a result of d2sp3 (or,
sp3d2), dsp2 and sp3hybridisation, respectively, of the central atom or ion. Some
trigonalbipyramidal complexes are also known which are formed when the central
metal center undergoes sp3d hybridization.
8. If the inner d-orbital’s, i.e., (n − 1) d-orbitals, are involved, the complex is called inner
orbital or low-spin complex,but if outer d-orbitals i.e. ndorbitals are used, the complex
is called outer orbital or high-spin complex.

The complex formation can be explained with help of some examples as follows.

(A) Coordination number 4

The most appropriate orbitals for this type of hybridisation with s orbital aredx2−y2, pxand
pyorbitals. The typical example is [Ni(CN)4]2-.
1. [Ni(CN)4]2-:In this complex ion, Ni is in +2 oxidation state and has coordination number
equal to 4. The two possible geometries for CN = 4 can be either tetrahedral and square
planar with sp3 and dsp2 hybridisation, respectively. For tetrahedral geometry, there
would be two unpaired electrons in the complex ion resulting in its magnetic moment µs
= 2.83 B.M. However, experiments reveal that [Ni(CN)4]2-is diamagnetic with µs= 0,
indicating that there are no unpaired electrons. This is possible only if two unpaired d-
electrons get paired up due to the energy available by the approaching ligands. This
makes one of the 3d orbitals vacant and available for hybridisation. Thus, the geometry
of the complex would be square planar due to dsp2hybridisation. The empty dsp2 hybrid
orbitals overlap with the fully filled orbitals of the ligands (CN− ion) to form the four
coordinate bonds.

Under the influence of a strong-field ligand like CN-, the unpaired electrons in the 3d-subshell
pair up, and the empty 3d orbital, 4s and two 4p orbitals hybridize to form four equivalent dsp2
orbitals. The four lone pairs from cyanide ligands occupy these dsp2orbitals to form square planar
and diamagnetic complex.

3d 4s 4p
Ni(II) ion

dsp2-hybridisation

3d 4s 4p
[Ni(CN)4]2-

2. [Ni(Cl)4]2-:In this complex, Niis present in +2 oxidation state with 4s and 4p vacant
orbitals available for sp3hybridisation. As a result, there will be two unpaired electrons
with magnetic moment μs= 0 or 2.83 BM. The experiments reveal that this complex ion

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is paramagnetic with μs= 2.83 BM. As a result, the geometry of the complex ion is
tetrahedral.

Since Cl- is a weak-field ligand, it does not have the tendency tair up electronsin the 3d-subshell.
The empty 4s and three 4p orbitals hybridize to form four equivalent sp3 orbitals. The four lone pairs
from Cl- ligands occupy these sp3 orbitals to form tetrahedral and paramagnetic complex.

(B) Coordination number 6

The most appropriate orbitals for hybridisation with s and p-orbitals aredz2and
dx2−y2orbitals. Depending upon the inner or outer d-orbitals used, therecan be two types of
complexes, i.e. outer orbital complex and inner orbitalcomplex, as illustrated below.

1. [Co(NH3)6]3+: In this complex, cobalt is in the +3 oxidation state, the magnetic moment
measurement indicates that the complex is diamagnetic with all electrons paired. This
indicates that the 3d electrons get paired up in presence of ammonia ligands and make
d-orbitals available for hybridisation. Thus, the complex ion is formed
byd2sp3hybridisation and has octahedral geometry.

In the presence of strong-field ligand like NH3, the pairing of electrons occurs in the 3dorbitals
in Co3+, making two 3dorbitals vacant. These two vacant 3d orbitals combine with one 4s
and three 4p orbitals, and hybridize to give six equivalent d2sp3hybridised orbitals directed
towards the corners of an octahedron.

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 Coordinate Compounds ….. By….. G. H. Reshi

The complex is diamagnetic due to the absence of any unpaired electron. Also, the inner (n-1)d
orbitals are used for bond formation, and thus, the complex is known as inner orbital or low-spin or
spin-paired complex.

2. [CoF6]3-:In this complex, cobalt is in the +3 oxidation state, andthe magnetic moment
measurements indicate that the complex is paramagnetic with unpaired electrons.
3d 4s 4p
Co atom

3d 4s 4p
Co(III) ion

Under the influence of the weak-field ligand F-, the electrons do not pair up. Therefore, one 4s,
three 4p and five 4d orbitals hybridize to form six hybrid orbitals, which accept lone pair of electrons
from six fluoride ligands to form an octahedral complex.

The complex is paramagnetic due to the presence of unpaired electrons. Also, the outer nd-
orbitals are used for bond formation, and thus, the complex is known as outer orbital or high-spin
or spin-free complex.

Notable points:

1. Complexes of the 4d and 5d transition metals (like Pd, Pt, Rh, Ir, etc.) in coordination number 4
always form square planar complexes, irrespective of the strength of ligand field.
e.g., [PdCl4]2-, [PtCl4]2-, [Pt(NH3)4]2+, [PdCl2(NH3)2]2+,etc. are all square planar
complexeswith dsp2hybridisation.
2. Metals in higher oxidation states (like Sc3+, V3+, Cr3+, Ti3+, etc.) always form inner orbital
complexes in coordination number 6, irrespective of the nature of the ligand.
e.g., [ScF6]3-, [TiF6]3-, [Ti(OH2)6]3+, [V(OH2)6]3+, [Cr(OH2)6]3+, [Cr(NH3)6]3+, etc. are all inner
2 3
orbital complexeswith d sp hybridisation.

Limitations of Valence Bond Theory

This theory gives a representation of metal-to-ligand bonding. However,there are many

shortcomings which are discussed below.

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1. This theory fails to account for the characteristic electronic spectra ofcoordination compounds.
2. This theory considers only the magnetic moment by spin but does nottake account of orbital
motion of electrons. As a result, there isdifference in the spin only magnetic moment,μsand the
experimental magnetic moment,μexp, values for many complexes.
3. It could not properly differentiate between the weak and strong field ligands.
4. It could not explain the stability of the complexes.
5. According to this theory, all square planar complexes of Ni2+ should bediamagnetic but actually
some square planar complexes of Ni2+ areknown to be paramagnetic. The valence bond theory
suggests thatthere should be excitation of one 3d electron to the vacant p-orbital toform inner
orbital square planar complex but the reason for thisexcitation has not been explained.

Crystal Field Theory (CFT)

The Crystal Field Theory was developed by H. Bethe (1929) and J. vanVleck (1932). The
crystal field theory (CFT) is an electrostatic model, which considers the metal-ligand bond to be
ionic arising purely from electrostatic interactions between the metal ion and the ligand. Since
these interactions are similar to those between the ions in a crystal, that is why it has been
named as crystal field theory (CFT).

In thecrystal field theory, the following assumptions are made:

1. Ligands are treated as point charges in case of anions or dipoles in case of neutral
molecules like H2O, NH3, etc.
2. There is no interaction between metal orbitals and ligand orbitals.
3. The five d orbitals in 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 lifted. It results in splitting of
the d orbitals. The pattern of splittingdepends upon the nature of the crystal field exerting
its influence on the metal center.
In most transition metal complexes, either six or four ligands surround the metal giving
octahedral, square planar or tetrahedral structures. In all these cases, the field produced by
the ligands is not spherically symmetrical. Thus, under the influence of the ligands, the five
degenerate d orbitalsof the metal ion will split into orbitals of different energies. This effect
is known as crystal field splitting or energy level splitting.

(a) Crystal field splitting in octahedral coordination complexes

Depending upon the orientation of the d-orbitals in space, these can bedivided into two
groups, viz. the axial d-orbitals, with their lobes along theaxes (dz2 and dx2−y2) and the non-
axial d-orbitals, with their lobes orientedbetween the axes (dxy, dyzand dxz).
Consider an octahedral complex, [ML6]n+, with central metal ion atcentre of the
octahedron and its ligands L at the six corners of the octahedron,pointed along the three
axes x, y and z.

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 Coordinate Compounds ….. By….. G. H. Reshi

Splitting of d-orbitals in octahedral crystal field

In the absence of ligands, the d-orbitals are degenerate. Now, if the ligands start
approaching the central metal ion, along thethree axes, the electrons in the axial orbitals
face greater repulsive forces ascompared to the electrons in the non-axial orbitals, i.e. the
energy of the axialorbitals gets increased, while that of non-axial orbitals gets
loweredrelative to the average energy in the spherical crystal field .As aresult, the degeneracy
of the five d-orbitals gets split up into two sets, viz.doubly degenerate, eg orbitals (dz2 and
dx2−y2)of higher energy and triply degenerate t2gorbitals (dxy, dyzand dxz).of lower energy.
Thedifference in the energy of the two sets of d-orbitals is denoted by ∆o(the subscript ‘o’ is
for octahedral) or 10Dqand is called crystal-field splitting energyor crystal-fieldstabilisation
energy (CFSE). It follows that the energy of egorbitals is 0.6∆o(or, 6Dq)above the
hypothetical degenerate d-orbitals, and the t2gorbitals is 0.4∆o(or, 4Dq)below the
hypothetical degenerate d-orbitals.
The crystal field splitting,∆o, depends on the number of factors , the most important
amongst which are the nature of the ligand andcharge on the metal ion. If it is easier for a
ligand to approach metal center and interact with it, then the extent of crystal field splitting
is high. Theligands which are able to cause only a small degree of crystal fieldsplitting are
called weak field ligands whereasthe ligands which causea large degree of crystal field
splitting are called strong field ligands. The strong ligands a give a higher value of ∆oand the
weak ones give a lower value. Ingeneral, some common ligands can be arranged in a series
in the order of increasingfield strength as given below:

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State Institute of Education, Kashmir
I-< Br-< S2-< SCN-<Cl-< F-< OH-< C2O42-< H2O < NCS-<EDTA4-
< NH3< en< o-phenanthroline< NO2-< CN-< CO

This arrangement of ligands in the order of their abilities to split the energies of the d-
orbitals is called the spectrochemical series. It is an experimentally determined series based
on the absorption of light by the complexes with different ligands.

When the first, second and third electrons enter the d-orbital, they occupy the t2g (lower
energy) orbitals one by one in accordance with the Hund’s rule. However, when the fourth
and the next electrons enter the d-orbitals, the two possible patterns of electron
distributions arise:

(i) the fourth and the next electron couldeither enter the t2g level and pair with an existing
electrons ( in against the Hund’s rule of maximum multiplicity).
(ii) the fourth and the next electron could avoid paying the price of the pairing energy by
occupying the higher eg orbitals in accordance with the Hund’s rule of maximum
multiplicity.

The exact path chosen by the electron depends upon the relative magnitude of
the crystal field splitting ∆oand the pairing energy, P(P represents the energy required
for electron pairing in a single orbital).

(a) If o < P,the fourth electron enters one of the eg orbitals giving the configurationt2g3
eg1. Ligands for which o< P are known as weak field ligands and form high spin
complexes.
(b) If o> P, it becomes more energetically favourable for the fourth electron to occupy a
t2g orbital with configuration t2g4eg0. Ligands which produce this effect are known as
strong field ligands and form low spin complexes.
On the basis of calculations, it has been shown that coordination entities with d4
to d7metal ion configurations are morestable for low spin state (strong ligand field)than
for the high spin state(weak ligand field).

Calculation of CFSE:

CFSE = (-0.4 + 0.6 ) o+

where′ ′ is the number of electrons occupying t2g orbital and ′ ′ electrons

occupying eg orbitals.′ is the number of paired electrons.

For example,
d1 configuration (t2g1), CFSE = -0.4o
d2 configuration (t2g2), CFSE = 2 × (-0.4) =-0.8o
d3 configuration (t2g3), CFSE = 3 × (-0.4) =-1.2o
d4 configuration (t2g3eg1), CFSE = 3 × (-0.4) + 0.6 =-0.6o
d4(low spin)configuration (t2g4eg0), CFSE = 4 × (-0.4) =-1.6o
d5 configuration (t2g3eg2), CFSE = 3 × (-0.4) + 2 × (0.6) =0.0o
d5(low spin)configuration (t2g5eg0), CFSE = 5 × (-0.4) =-2.0o
d6 configuration (t2g4eg2), CFSE = 4 × (-0.4) + 2 × (0.6) =-0.4o

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 Coordinate Compounds ….. By….. G. H. Reshi
6 6 0
d (low spin)configuration (t2g eg ), CFSE = 6 × (-0.4) =-2.4o

(b) Crystal field splitting in tetrahedral coordination complexes

A tetrahedral arrangement can be visualised by placing the four corners of
thetetrahedron at the alternate corners of a cube. Four ligands located at the alternate
corners of a cube are lying between thethree axes and hence interact more with the d-
orbitals lying between the axes.
The splitting pattern for the tetrahedral complexes is just the reverse of the splitting
pattern of the octahedral complexes, i.e., the three-fold degenerate set,t2,has higher energy
than the two-fold degenerate set, e. The differencein energy between the two sets of d-
orbitals for a tetrahedral complex isrepresented as Δt. Since there is lesser interaction of the
d-orbitals with theligands along any of the axes because of the presence of only four ligands
ascompared to greater interaction of six ligands in an octahedral complex, Δtisless than
Δ0(Δt=-4/9 Δ0.) The minus sign signifies the reverseorder of splitting in tetrahedral
complexes in comparison to octahedralcomplexes. Consequently, theorbital splitting
energies arenot sufficiently large for forcingpairing and, therefore, low spinconfigurations
are rarelyobserved. The crystal field splitting energy fora tetrahedral complex can be
calculated as,

CFSE = (0.4 - 0.6 ) o+

where ′ ′ is the number of electrons occupying t2 orbital and ′ ′ electrons

occupying eorbitals.′ is the number of paired electrons.

Splitting of d-orbitals in a tetrahedral crystal field

Applications of Crystal Field Theory

1. Colour of Transition Metal Complexes

When white light falls on a transition metal complex, the complex mayabsorb some
portion of it and the remaining portion is reflected or transmittedback.Thecolour of the
transmitted light is different from the colour of theabsorbed light and is known as the
complementary colourof the absorbedlight. The colour of the transition metal complex is
the colour of thistransmitted light. Table 9.3 shows the relation between the colour of
theabsorbed and the transmitted light.

Table 9.3.Colour of the absorbed and transmitted light

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State Institute of Education, Kashmir
Colour of the absorbed light Wavelength of the absorbed Colour of the transmitted
light light
(Å)
Violet 4000–4500 Yellow green
Blue 4500–4800 Yellow
Green-blue 4800–4900 Orange
Blue-green 4900–5000 Red
Green 5000–5600 Violet
Yellow-green 5600–5800 Violet
Yellow 5800–5900 Blue
Orange 5900–6050 Green-blue
Red 6050–7500 Blue-green

Origin of Colour: In a transition metal complex, the degeneracy of the five d-orbitalsis
splitted under the influence of the ligands to form two sets oforbitals ─ lower energy t2g set
and higher-energy egset of orbitals.
The difference in energy between these two levels (∆O) is very small andcan be covered
even by the low-energy radiations of the visible region( = ) .Thus, when the electrons
from the low energy set of orbitals is excited to thehigh energy set of orbitals due to
absorption of light of suitable wavelength inthe visible region, the complex appears
coloured. This transition is known asd-d-transition. Since ∆O varies with the nature of metal
ion, ligands and thegeometries of complexes, the absorption of light of selected wavelength
alsovaries accordingly.
Consider, for example, the complex[Ti(H2O)6]3+, which is violet in colour. This is an
octahedral complexwhere the single electron (Ti3+ is a 3d1 system) in the metal d orbital isin
the t2g level in the ground state of the complex. The next higher stateavailable for the
electron is the empty eg level. On irradiationwith visible light,the electron wouldget excited
from t2g level to the eg level (t2g1eg0→t2g0eg1).Consequently, the complex appears violet in
colour. However, the complex becomes colourless on heating due to loss of water
molecules. Similarly, Cu(II) ion in aqueous solution, i.e., [Cu(H2O)6]2+ is blue in colour, as red
light corresponding to = 6000Å is being absorbed.

d-d transition in [Ti(H2O)6]3+ complex ion

Colour of the absorbed light varies with the nature ofligands. Thus, as the ∆O increases
from H2O < NH3 < CN- ligands, the colourof the complexes [Co(NH3)6]3+ and [Co(CN)6]3−
varies from blue to yellowrespectively.

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 Coordinate Compounds ….. By….. G. H. Reshi
The value of ∆O also varies with oxidation state of the metal center;thus, [V(H2O)6]2+
appears violet but [V(H2O)6]3+ appears yellow.
The transition metal complexes with empty (d0) or completely filled (d10)d-orbitalsare
colourless due to absence of any d-d transitions. Thus,complexes of Sc3+ (d0), Ti4+ (d0), Cu+
(d0), Zn2+ (d10), Ag+ (d10), Cd2+ (d10)and Hg2+ (d10) etc, are colourless.

2. Magnetic Properties of Transition Metal Complexes

The number of unpaired electrons in a transition metal complex can bedetermined with
the help of crystal field theory. It can be seen that for acentral metal ion with d4 to d8
configurations, the number of unpairedelectrons are different in high-spin and low-spin
octahedral complexes. As aresult, their magnetic moments calculated by the spin-only
formula,µs= ( + 2)BM also comes different. Thus, it helps indetermining the
diamagnetic (all paired electrons) and paramagnetic(unpaired electrons) character of the
complexes.

Limitations of Crystal Field Theory

1. Crystal field theory considers only the d-orbitals of the metal ion andgives no
consideration to the other orbitals of the metal atom (s, px, pyand pz) and the ligand π-
orbitals. Thus, it cannot explain the π-ligandorbital’s dependent properties of the
complexes.
2. It does not consider the formation of π-bonding in the complexes.
3. It gives no satisfactory explanation for the relative strength of theligands in the
spectrochemical series.
4. This theory considers the metal and ligand interaction as a purely ionicand doesn’t
consider the partial covalent nature of the metal-ligand bonds.

Bonding in Metal Carbonyls

Metal carbonyls are the organometallic compounds (which contain at least one metal-
carbon bond) in which carbon monoxide (CO) acts as a ligand. The first metal carbonyls,
Ni(CO)4 and Fe(CO)5, were discovered in 1890 and 1891, respectively, and now carbonyl
derivatives of at least one type are known for all transition metals. The homoleptic
carbonyls (compounds containing carbonyl ligandsonly) are formed by most of the
transition metals. These carbonyls are of the type M(CO)x, and have simple well-defined
structures.Tetracarbonylnickel(0), Ni(CO)4, istetrahedral, pentacarbonyliron(0), Fe(CO)5, is
trigonalbipyramidal whilehexacarbonyl chromium(0), Cr(CO)6 is octahedral.

There are numerous polynuclear carbonyls that homonuclear, such as Fe3(CO)12 or

heteronuclear, such as MnRe(CO)10. In these compounds, there are not only linear M-C_M

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groups but also either M-M bonds or M_M bonds with bridging carbonyls. For example,
decacarbonyldimanganese(0), Mn2(CO)10, is made up of two square pyramidal Mn(CO)5
units joined by an M-M bond and octacarbonyldicobalt(0), Co2(CO)8, has a Co – Co bond
bridged by two CO groups.

The metal-carbon bond in metal carbonylspossess both σ and π character. The M–C σ-
bondis formed by the donation of lone pair of electronson the carbonyl carbon into a
vacant orbital ofthe metal. The M–C π-bond is formed by thedonation of a pair of electrons
from a filled dπ-orbitalof metal into the vacant antibonding π*-orbital ofcarbon monoxide.
The effect of σ-bond formation strengthens the π-bond and vice-versa. This metal to ligand
bondingis called synergic effect, which strengthens thebond between CO and the metal.

Synergic bonding interactions in a carbonyl complex

Stability of Coordination Compounds

Most of the complexes are highly stable. The stability of a complex in solution means
the degree of dissociation between the metal ion and the ligands involved in the state of
equilibrium. The extent of dissociaton and hence the thermodynamic stability of the
complex ion depends upon the strength of the metal-ligand bonding. Stronger the
interaction, higher will be the stability of the complex. Consider the general reaction for
the formation of the coordination complex,

M + nL→[MLn]

where a+, b- and c+ are the charges on the metal, ligand and complex, respectively.

The stability constant can be written as,

The overall reaction proceeds through various steps with stability constants K1, K2, K3, ·····,
Kn foreach step as represented below:

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 Coordinate Compounds ….. By….. G. H. Reshi

In these steps of reaction, K1, K2, K3, ····· Kn are called as “stepwise stability constants” and
the stability constant for the overall reaction is given as,

n = K1 × K2 × K3 × ····· × Kn

Thus the overall stability constant for the formationof the complex [MLn]may be written as,

ncan be alternatively put as,

log n = logK1 + logK2 + logK3 + ····· + logKn

log n may be used as a measure of stability of the complex. For example, for [Cu(NH3)4]2+,
the four constants are:

log 4= logK1 + logK2 + logK3 + logK4

log 4= 4.0 + 3.2 + 2.7 + 2.0

log 4= 11.9

The addition of the four amine groups to copper shows a pattern found for most of the
stability constants. The successive stability constants decrease with addition of each amine
group.

For [Cd(NH3)4]2+
log 4= 2.6 + 2.1 + 1.4 + 0.9

log 4= 7.0

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Thus,log 4values of [Cu(NH3)4]2+ and [Cd(NH3)4]2+ complexes indicate that [Cu(NH3)4]2+ is
more satble than [Cd(NH3)4]2+ complex. That is why, Cu2+ does not form precipitate as CuS
when H2S is passed through the solution containing [Cu(NH3)4]2+, while Cd2+ ions form
precipitate as CdS because of instability of [Cd(NH3)4]2+ complex ions.

The reciprocal of the stability or formation constant gives the instability constant or
dissociation constant of a coordination compound. Thus,
1
dissociation constant of complex =
stability constant

Importance and Applications of Coordination Compounds

Coordination compounds are found in living systems and have many uses in the home,in
industry and in medicine. The importance and applications of coordination compounds can
be summarized as follows:

1. Metallurgy

The extraction of silver and gold by the formation of cyanide complexes and
thepurification of nickel by converting the metal to the gaseous compound Ni(CO)4
aretypical examples of the use of coordination compounds in metallurgical processes.

2. Chelation Therapy

Chelation therapy is used in the treatment of lead poisoning. EDTA, when injected
intravenously into the bloodstream, traps lead as an EDTA complex, which is being flushed
out of the bodywith the urine. Other metals, such as alumunium, selenium, arsenic,
mercury, etc. can also be removed using chelating agents.

3. Chemotherapy

Several platinum-containing coordination compounds, including cisplatin

[Pt(NH3)2Cl2]and carboplatin [Pt(NH3)2(OCO)2C4H6], can effectively inhibit the growth of
cancerouscells.The mechanism for the action of cisplatin is the chelation of DNA, the
moleculethat contains the genetic code. During cell division, the double-stranded DNA
unwindsinto two single strands, which must be accurately copied for the new cells to be
identicalto their parent cell. X-ray studies show that cisplatin binds to DNA by formingcross-
links in which the two chlorides on cisplatin are replaced by nitrogen atoms inthe adjacent
guanine bases on the same strand of the DNA(Guanine is one of the fourbases in DNA). This
causes a bend in the double-stranded structure at the binding site.It is believed that this
structural distortion is a key factor in inhibiting replication. Thedamaged cell is then
destroyed by the body’s immune system. Because the binding ofcisplatin to DNA requires
both Cl atoms to be on the same side of the complex, thetransisomer of the compound is
totally ineffective as an anticancer drug.

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 Coordinate Compounds ….. By….. G. H. Reshi

4. Chemical Analysis

Although EDTA has a great affinity for a large number of metal ions (especially +2 and+3
ions), other chelates are more selective in binding. Dimethylglyoxime, for example,forms an
insoluble brick-red solid with Ni2+ and an insoluble bright-yellow solid withPd2+. These
characteristic colors are used in qualitative analysis to identify nickel andpalladium.
Furthermore, the quantities of ions present can be determined by gravimetricanalysis.For
instance, to a solution containing Ni2+ ions, say, we add anexcess of dimethylglyoxime
reagent, and a brick-red precipitate forms. The precipitate isthen filtered, dried, and
weighed. Knowing the formula of the complex formed,we can readily calculate the amount
of nickel in the original solution.

The presence of iron ions (Fe3+) can be detected by the addition of potassium ferrocyanide solutions,
which results in the formation of Prussian blue complex.

Similarly, Co2+ ions can be detected by the addition of ammonium thiocyanate solution, which
results in the formation of blue colour solution due to the formation of the following complex.

5. Detergents

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The cleansing action of soap in hard water is hampered by the reaction of the Ca2+ions
in the water with the soap molecules to form insoluble salts or curds. Hardness of water is
estimated by simple titration with Na2EDTA.The Ca2+ and Mg2+ ions form stable complexes
with EDTA. Theselective estimation of these ions can be done due to difference inthe
stability constants of calcium and magnesium complexes.

6. Electroplating

Coordination compounds of silver, gold and copper can be used for electroplating
articles of other metals with these metals. For example, in electroplating of silver, gold and
copper, the complexes K[Ag(CN)2],K[Au(CN)2] and K3[Cu(CN)4] are employed as an
electrolyte, respectively.

7. Catalysis

Coordination compounds are used as catalysts for many industrialprocesses. Examples

include rhodium complex, [(Ph3P)3RhCl], aWilkinson catalyst, is used for the hydrogenation
of alkenes. Similarly, the Zeigler-Natta catalyst (TiCl4 and trialkylaluminium) is used as a
catalyst in the formation of polyethene.

8. Biological importance

Coordination compounds are of great importance in biologicalsystems. The pigment

responsible for photosynthesis, chlorophyll,is a coordination compound of Mg2+.
Hemoglobin, the redpigment of blood, which acts as oxygen carrier is a
coordinationcompound of Fe2+. Vitamin B12, cyanocobalamine, the anti–pernicious anemia
factor, is a coordination compound of Co3+.

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