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114 Coordination Compounds

COORDINATION
COMPOUNDS
Chapter 09
Percentage of Questions in Last 34 Years' in NEET / AIPMT from this Chapter
%
C. 1 0

A. VBT, CFT 48%

B. Introduction, Nomenclature, Isomerism 42%

A. 48% B. 42%
C. Organometallic Compounds 10%

WHAT DO YOU WANT TO KNOW? 9.4.5 Geometrical Isomerism

9.4.6 Optical Isomerism
9.0 INTRODUCTION 9.5 BONDING IN COORDINATION COMPOUNDS
9.1 WERNER’S THEORY OF COORDINATION 9.5.1 Valance Bond Theory
COMPOUNDS 9.5.2 Magnetic Properties of Coordination
9.2 DEFINITION OF SOME IMPORTANT Compounds
TERM PERTAINING TO COORDINATION 9.5.3 Limitations in Valence Bond Theory
COMPOUNDS 9.5.4 Cristal Field Theory
9.3 NOMENCLATURE OF COORDINATION 9.5.5 Colour in Coordination Compounds
COMPOUNDS 9.5.6 Limitations of Crystal Field Theory Page
9.3.1 Writing the Formulas of Mononuclear 9.6 BONDING IN METAL CARBONYLS
Coordination Entities 9.7 STABILITY OF COORDINATION COMPOUNDS
9.3.2 Writing the Name of Mononuclear 9.8 APPLICATIONS OF COORDINATION AND
Coordination Compounds ORGANOMETALLIC COMPOUNDS
9.3.3 Writing the Name of Polynuclear
9.9 SYNOPSIS
Coordination Compounds
9.10 MISCELLANEOUS Questions from NCERT
9.4 ISOMERISM IN COORDINATION 9.11 NCERT Exemplar Questions
COMPOUNDS 9.12 Assertion-Reason and Statement
9.4.1 Ionisation Isomerism Based Questions from NCERT
9.4.2 Solvate Hydrate Isomerism 9.13 Matrix Based Questions
9.4.3 Linkage Isomerism 9.14 ARCHIVE QUESTIONS
9.4.4 Coordination Isomerism 9.15 ANSWER KEY
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Coordination Compounds 115

Stability

Colour COORDINATION COMPOUNDS Applications

VBT CFT

Features Tetrahedral Octahedral

Bonding in Field Field
metal
Geometry
carbonyls
Spectrochemical Series
Inner/Outer

Weak field Strong Field

High/Low spin

Magnetic Properties

ISOMERISM
Structural Stereo
Isomerism Isomerism
Ionisation
Linkage Geometrical (cis-trans) Optical (object - mirror image)
Hydrate
Square planar complexes Octahedral complexes Criteria
Co-ordination
Ma2b2 Ma4b2 Examples
Ma2bc Ma3b3
M(XY)2 M(XX)2b2

M(XX)2bc

Double salts MOLECULAR Complex salts

K2SO4.Al2(SO4)3.24H2O ADDITION K4[Fe(CN)6]
COMPOUNDS
Or
Co-ordination compounds
Complex ion Neutral
EAN rule Werner’s theory
Monodentate Central metal ion Neutral
Application Assumptions
Bidentate Co-ordination number Neutral
Examples
Tridentate Ligands
Nomenclature Explanations
Polydentate Chelating agents
Ambidentate Co-ordination sphere Cationic Anionic Neutral
complexes complexes complexes
Chelating Ionisation sphere
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116 Coordination Compounds

9.0 INTRODUCTION P.No.: 244

 The concept of co-ordination compounds arises from the complex formation tendency of transition elements.
 These compounds play a vital role in our lives, as chlorophyll of plants, vitamin B12 and haemoglobin of animal
blood are the co-ordination compounds of Mg, Co and Fe respectively.
 The co-ordination compounds play important role in analytical chemistry, polymerisation reactions, metallurgy
and refining of metals, photography, water purification etc.
 Co-ordination compounds also find many applications in electroplating, textile dyeing and medicinal chemistry.

ADDITION COMPOUNDS :
 They are formed by the combination of two or more stable compounds in stoichiometric ratio.
Addition Compounds

Double salts Coordination compounds

(Complexes)
 Double salts : Those addition compounds which lose their identity in solutions are called double salts. For
example, when K2SO4 solution is added to Al2 (SO4)3 solution, the species formed when dissolved in water gives
tests of K+, Al3+ and SO42– ions.
K2SO4 + Al2(SO4)3 + 24H2O  K2SO4.Al2(SO4)3.24H2O (aq.)  2K+ (aq.) + 2Al+3 (aq.) + 4SO42– (aq.)
Other examples are carnallite (KCl. MgCl2 . 6H2O), Mohr’s salt [FeSO4 . (NH4)2SO4 . 6H2O], potash alum
[KAl(SO4)2.12H2O] etc.

 COORDINATION COMPOUNDS : Those addition compounds which retain their identity (i.e. doesn’t lose
their identity) in solution are called coordination compounds. For example, when KCN solution is added to
Fe(CN)2 solution, the species formed when dissolved in water no longer gives tests of Fe2+ and CN–.
Fe(CN)2 + 4KCN  Fe(CN)2 . 4KCN or K4 [Fe(CN)6] (aq.)   4K+ (aq.) + [Fe(CN)6]4– (aq.)
Other examples are,  [Cu(NH3)4]2+ (aq.) + SO42– (aq.)
[Cu(NH3)4]SO4 (aq.) 
 2K+ (aq.) + [Zn(CN)4]2– (aq.)
K2[Zn(CN)4] (aq.) 
1. Coordination compounds are also acid-base adducts and are frequently called complexes or, if charged then
complex ions.
2. Coordination compound is defined as a species in which metal atom or ion is attached to group of neutral
molecules / ions by coordinate covalent bonds.

9.1 WERNER’S THEORY OF COORDINATION COMPOUNDS P.No.: 244

 Several theories were proposed but none of them could satisfactorily explain the observed properties of
Co(III) ammines and of other similar compounds like Pt(IV) ammines which had been prepared by them. It
was only in 1893, that Werner presented a theory known as Werner's coordination theory which could
explain all the observed properties of complex compounds. According to him most elements exhibit two
types of valencies : (a) Primary valency and (b) Secondary valency.
 Primary valency :
1. This corresponds to the oxidation state of the metal ion.
2. This is also called as the principle, ionisable or ionic valency.
3. It is satisfied by the negative ions and its attachment with the central metal ion is shown by dotted
lines.
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Coordination Compounds 117

 Secondary or auxiliary valency :
1. It is also termed as the coordination number (usually abbreviated as CN) of the central metal ion.
It is non-ionic or non-ionisable (i.e. coordinate covalent bond type).
2. This is satisfied by either negative ions or neutral molecules having lone pair of electrons (e.g.,
H2O, NH3 etc.) or even sometimes by some positive groups.
3. The ligands which satisfy the coordination number are directly attached to the metal atom or ion
and shown by thick lines.
4. Every element tends to satisfy both its primary and secondary valencies. In order to meet this
requirement a negative ion may often show a dual behaviour, i.e. it may satisfy both primary and
secondary valencies since in every case the fulfillment of coordination number of the central
metal ion appears essential. This dual behaviour is represented by both thick and dotted lines. For
example, [CoCl(H2O)5]Cl2 is represented as
H2O
H2O H2O
Cl Co Cl
Cl H2O
H2O
5. Every metal has a fixed number of secondary valencies, e.g., cobalt(III) and platinum(IV) have
six secondary valencies and copper(II) four.
6. The coordination number of a metal in a particular oxidation state is generally fixed but certain
oxidation states of certain metals have found to possess more than one coordination number.
7. The ions/groups bound by the secondary valencies have characteristic spatial arrangements corre-
sponding to different coordination number. In the modern terminology, such spatial arrangements
are called coordination polyhedra and various possibilities are
C.N. = 2 linear C.N. = 3 Triangular
C.N. = 4 tetrahedral or square planar C.N. = 6 octahedral.
8. To distinguish between the two types of valencies, Werner introduced the square brackets [ ] to
enclose those atoms making up the coordination complex and which are, therefore, not ionized.
9. On the basis of the above postulates Werner formulated the coordination compounds, CoCl3 .
6NH3, CoCl3 . 5NH3 and CoCl3 . 4NH3 as : [Co(NH3)6]Cl3, [Co(NH3)5Cl]Cl2 and [Co(NH3)4Cl2]Cl
respectively; the species within the square brackets being the coordination entities (complexes)
and the ions outside the square brackets the counter ions. He further postulated that octahedral,
square, planar and tetrahedral geometrical shapes are more common in coordination compounds
of transition metals. Thus, [Co(NH3)6]3+, [CoCl(NH3)5]2+, [CoCl2(NH3)4]+ are octahedral entities,
while [Ni(CO)4] and [PtCl4]2– are tetrahedral and square-planar respectively.
Secondary valency
S.No. Werner complex Modern notation Ionisation Primary valency satisfied by
satisfied by
1 CoCl3.6NH3 [Co(NH3)6]Cl3 [Co(NH3)6]3++3Cl– six (NH3) three (Cl–)
three (Cl–) including one (Cl–)
2 CoCl3.5NH3 [Co(NH3)5Cl]Cl2 [Co(NH3)5Cl]2++2Cl– five (NH3) and one (Cl–)
with dual nature
three (Cl–) including
3 CoCl3.4NH3 [Co(NH3)4Cl2]Cl [Co(NH3)4Cl2]++ Cl– four (NH3) and two (Cl–)
two (Cl–) with dual nature
4 CoCl3.3NH3 [Co(NH3)3Cl3] [Co(NH3)3Cl3] three (NH3) and three (Cl–) three (Cl–) all with dual nature
10. From the above table it is clear that (i) the solution conductivities of complexes 1, 2 and 3
correspond to 1 : 3, 1 : 2 and 1 : 1 electrolyte respectively and thus the increasing order of the
conductivity can be represented as CoCl3.3NH3 < CoCl3. 4NH3 < CoCl3.5NH3 < CoCl3.6NH3 and
(ii) the complexes 1, 2 and 3 will react with silver nitrate and give 3, 2 and 1 mole of the white
precipitate of silver chloride respectively.
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118 Coordination Compounds

NCERT LIKE PROBLEM NCERT P.No.-244

Consider the following complexes :
(i) K2PtCl6 (ii) PtCl4 . 2NH3 (iii) PtCl4 . 3NH3 (iv) PtCl4 . 5NH3
their electrical conductance in aqueous solutions are :
(A) 256, 0, 97, 404 (B) 404, 0, 97, 256 (C) 256, 97, 0, 404 (D) 404, 97, 256, 0

(A)
The electrical conductance of the complexes depend upon the number of ions given by them in the aqueous
solutions.

(i) K2[PtCl6]  aq
 + 2–
 2K (aq) + [PtCl6] (aq)

(ii) [Pt(NH3)2Cl4] aq

 [Pt(NH3)2Cl4] (aq)

(iii) [Pt(NH3)3Cl3]Cl aq
 + –
 [Pt(NH3)3Cl3] (aq) + Cl (aq)

(iv) [Pt(NH3)5Cl]Cl3  aq
 3+
 [Pt(NH3)5Cl] + 3Cl
–

Complex Number of ions Expected electrical conductance

(i) K2[PtCl6] 3 256
(ii) [Pt(NH3)2Cl4] 0 0
(iii) [Pt(NH3)3Cl3]Cl 2 97
(iv) [Pt(NH3)5Cl]Cl3 4 404
So, the correct option is (A).

01 (3) 1 (4) 5
7. An excess of AgNO3 is added to 100 mL of a 0.01 M
1. Which of the following has the highest molar conductivity solution of dichlorotetraaquachromium (III) chloride. The
in solution? number of moles of AgCl precipitated would be:
(1) [Pt(NH3)6]Cl4 (2) [Pt(NH3)5Cl]Cl3 (1) 0.002 (2) 0.001
(3) [Pt(NH3)4Cl2]Cl2 (4) [Pt(NH3)3Cl3]Cl (3) 0.003 (4) 0.01
2. An imperfect complex of a complex compound is 100% 8. One mole of complex compound Co(NH3)5Cl 3 gives 3
ionized; the compound is called: moles of ions on dissolution in water. One mole of same
(1) acid salt (2) complex salt complex reacts with two moles of AgNO3 to yield two
moles of AgCl(s). The complex is:
(3) double salt (4) normal salt
(1) [Co(NH3)4Cl2]Cl.NH3
3. Some salts although containing two different metallic
elements give test for one of them in solution. Such salts (2) [Co(NH3)4Cl]Cl2.NH3
are: (3) [Co(NH3)5Cl]Cl2
(1) double salts (2) complex salts (4) [Co(NH3)3Cl3].2NH3
(3) normal salts (4) none of these 9. Formation of complex compound can be detected by
4. Which of the following will exhibit maximum ionic (1) Change in colour
conductivity? (2) Change in solubility
(1) [Co(NH3)6]Cl3 (2) [Cu(NH3)4]Cl2 (3) Change in pH
(3) [Ni(CO)4] (4) K4[Fe(CN)6] (4) Change in electrical conductivity
5. Aqueous solution of which of the following complexes 10. Which of the following is the most likely structure of
would exhibit the highest molar conductance? CrCl3.6H2O, if 1/3 of total chlorine of the compound is
(1) K4[Fe(CN)6] (2) K2[PtCl4] precipitated by adding AgNO3 to its aqueous solution:
(3) [Cr(NH3)3Cl3] (4) [Co(NH3)6]Cl3 (1) CrCl3·6H2O
6. Number of ions produced when [Cu(NH 3 ) 4 ]Cl 2 is (2) [Cr(H2O)3Cl3](H2O)3
dissolved in water is/are (3) [CrCl2(H2O)4]Cl2H2O
(1) 3 (2) 2 (4) [CrCl.(H2O)5]Cl2H2O

sdfs
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Coordination Compounds 119

9.2 P.No.: 247

 Effective Atomic Number Rule given by Sidgwick :

 Effective Atomic Number (EAN) = No. of electron present on the metal atom/ion + No. of electrons
donated by ligands to it.
OR
 Effective Atomic Number (EAN) = Atomic no. of central metal – Oxidation state of central metal +
No. of electrons donated by ligands.
 The complexes in which the EAN of the central atom equals the atomic number of the next noble gas,
are found to be extra stable.
Note : The EAN rule is generally found to be not valid in case of most of the complexes but in case of metal
carbonyls this rule is found to be valid in all cases except one or two exceptions.

NCERT LIKE PROBLEM NCERT P.No.-247

Calculate the effective atomic number of the metal atoms in the following complexes / complex ions.
(a) [Cr(CO)6] (b) [Fe(CN)6]3– (c) [Co(CN)6]4– (d) [Ni(NH3)6]2+
[Cr = 24 ; Fe = 26; Co = 27 and Ni = 28 as atomic numbers]

(a) 36 (b) 35 (c) 37 (d) 38

EAN = Number of electrons in metal atom or ion + Number of electrons donated by ligands to metal.
(a) [Cr0(CO)6] ; EAN = 24 + 12 = 36 ; (b) [FeIII(CN)6]3– ; EAN = 23 + 12 = 35
(c) [CoII(CN)6]4–; EAN = 25 + 12 = 37 ; (d) [NiII(NH3)6]2+; EAN = 26 + 12 = 38

COORDINATION ENTITY / COORDINATION SPHERE P.No.: 247

 A coordination entity constitutes a central atom/ion, usually of a metal, to which are attached a fixed
number of other atoms or groups each of which is called a ligand. Ligand may be neutral or charged.
Examples being: [Co(NH3)6]3+, [PtCl4]2–, [Fe(CN)6]3–, [NiCl2(OH2)4].
 The central atom / ion and the ligands attached to it are enclosed in square bracket and is collectively called
as coordination sphere.
Note : The remaining ions apart from complex ions i.e. outside the coordination sphere are called counter
ions, free ions or ionisable ions. For example, in K4[Fe(CN)6], the potassium is counter ion of coordina-
tion entity [Fe(CN)6]4–.

CENTRAL ATOM / ION P.No.: 247

 In a coordination entity–the atom / ion around which a fixed number of ligands are bound in a definite
geometrical arrangement, is called the central atom or ion. For example, the central atom / ion in the
coordination entities : [NiCl2(OH2)4], [CoCl(NH3)5]2+ and [Fe(CN)6]3– are Ni2+, Co3+ and Fe3+, respectively.
 These central atoms / ions are also referred to as Lewis acids since they accept lone pairs from the ligands.

LIGANDS P.No.: 247

 The neutral molecules, anions or cations which are directly linked with central metal atom or ion in the
coordination entity are called ligands.
 These may be simple ions such as Br–, small molecules such as H2O or NH3, larger molecules such as
H2NCH2CH2NH2 or N(CH2CH2NH2)3 or even macromolecules such as proteins.
 When a ligand is attached to a metal ion through a single donor atom, as with Cl–, H2O or NH3, the ligand is
said to be unidentate. Similarly when a ligand is bound through two donor atoms (in a single ligand), as in
H2NCH2CH2NH2 (ethane-1, 2-diamine) or C2O42– (oxalate), the ligand is said to be bidentate and when
several donor atoms are present in a single ligand as in N (CH2CH2NH2)3 or ethylenediaminetetraacetic acid
(EDTA), the ligand is said to be polydentate.
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120 Coordination Compounds

CHELATE LIGAND P.No.: 247

 Chelate ligand is a di or polydentate ligand which uses its two or more donor atoms to bind a single metal
ion producing a ring. The complex formed is referred to as a chelate complex and the process of chelate
formation is called chelation. The number of such ligating groups is called the denticity of the ligand.
Chelate rings may have any number of atoms; the most common contain five or six atoms, including the
metal ion. Smaller rings have smaller angles and distances that lead to strain; larger rings frequently result
in crowding both within the ring and between adjoining ligands. Some ligands can form more than one ring;
ethylene diaminetetracetate (EDTA) can form five by using the four carboxylate groups and the two amine
nitrogens as given in the structures.
–
O H—O H 2

H3C — C == N N == C — CH3 Cl N
2+
Ni CH 2
Pt
H3C — C == N N == C — CH3 N CH
Cl 2

– H2
O—H O
 The chelate complexes are more stable than similar complexes containing unidentate ligands. The greater
stability of the chelate complex in comparison to normal complex is called chelate effect. For example,
 [Ni(NH3)6]2+ (aq)
Ni2+ (aq) + 6 NH3 (aq)  Kformation = 108
Ni2+ (aq) + 3 NH2CH2CH2NH2(aq)   [Ni(en)3]2+ (aq) Kformation = 1018
The five and six membered rings are more stable.

DENTICITY AND CHELATION P.No.: 247

 Common Monodentate Ligands

Common Name IUPAC Name Formula

methyl isocyanide methylisocyanide CH3NC
triphenyl phosphine triphenyl phosphine/triphenyl phosphane PPh 3
pyridine pyridine C5H5N (py)
ammonia ammine NH3
methyl amine methylamine MeNH 2
water aqua or aquo H2 O
carbonyl carbonyl CO
thiocarbonyl thiocarbonyl CS
nitrosyl nitrosyl NO
fluoro fluoro or fluorido* F–
chloro chloro or chlorido* Cl–
bromo bromo or bromido* Br–
iodo iodo or iodido* I–
cyano cyanido or cyanido-C* (C-bonded) CN–
isocyano isocyanido or cyanido-N* (N-bonded) NC–
thiocyano thiocyanato-S(S-bonded) SCN–
isothiocyano thiocyanato-N(N-bonded) NCS–
cyanato (cyanate) cyanato-O (O-bonded) OCN–
isocyanato (isocyanate) cyanato-N (N-bonded) NCO–
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Coordination Compounds 121

NCO
hydroxo hydroxo or hydroxido* OH–
nitro nitrito–N (N–bonded) NO2–
nitrito nitrito–O (O–bonded) ONO–
nitrate nitrato NO3–
amido amido NH2–
imido imido NH2–
nitride nitrido N3–
azido azido N3 –
hydride hydrido H–
oxide oxido O2–
peroxide peroxido O22–
superoxide superoxido O2 –
acetate acetato CH3COO –
sulphate sulphato SO42–
thiosulphate thiosulphato S2O 32–
sulphite sulphito SO32–
hydrogen sulphite hydrogensulphito HSO3–
sulphide sulphido or thio S2–
hydrogen sulphide hydrogensulphido or mercapto HS–
thionitrito thionitrito (NOS)–
nitrosylium nitrosylium or nitrosonium NO+
nitronium nitronium NO2+
* The 2004 IUPAC draft recommends that anionic ligands will end with-ido.

 Common Chelating Amines

Chelating
Common Name IUPAC Name Abbreviation Formula
Points
1,2-ethanediamine/
bidentate ethylenediamine en NH2,CH2CH2NH2
ethane-1,2-diamine
NH2–CH–CH2–NH2
bidentate propanediamine 1,2-propanediamine pn
CH3
[N-(2-aminoethyl)-1
tridentate diethylenetriamine 2-ethanediamine or dien NH2CH2CH2NHCH2CH2NH2
diethylenetriamine
triethylenetetraamine trien NH 2CH 2CH 2NHCH 2CH 2
tetradenate NHCH2CH2NH2
tren NH2CH2CH2NCH2CH2NH2
triaminotriethylamine
CH2CH2NH 2
1,4,7,10 pentaazatridecane NH 2CH 2CH 2NHCH 2CH 2
pentadentate tetraethylenepentaamine
or tetraethylenepentaamine NHCH2CH2NHCH 2CH2NH2
– –
1,2–ethanediyl (dinitrilo) OOCH2C CH2COO
hexadentate ethylenediaminetetraacetate tetraacetate or EDTA NCH2CH2N
ethylenediaminetetraacetate –
OOCH2C CH2COO–
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122 Coordination Compounds

FLEXIDENTATE LIGAND P.No.: 247

 It is not necessary that all the donor items present in the polydentate ligands should form coordinate bonds
with the central metal atom or ion i.e. a polydentate ligand which is found to have different denticity in
different coordination compounds is called a flexidentate ligand. Note that in a particular complex denticity
of a particular ligand is fixed, it can not be flexible in the same compound.
 EDTA can act as hexa, penta as well as tetra dentate ligand. For example ; EDTA usually acts as hexadentate
ligand but in [Cr(III)(OH)(EDTA)]2– and [Co(III)Br(EDTA)]2– as pentadentate and in [Pd(II)H2(EDTA)]0 as
a tetradentate ligand.
 Sulphate ion, SO42– can also be mono or bi dentate ligand. For example ; O

+
+
NH 3 S
en
O O O O
NH3
Co3+ S Co
3+
O
O O NH3 NH3
en
NH3

AMBIDENTATE LIGAND P.No.: 247

 Ligands which can ligate through two different atoms present in it are called ambidentate ligands.
Examples of such ligands are the CN–, NO2– and SCN¯ ions. NO2– ion can coordinate through either the
nitrogen or the oxygen atoms to a central metal atom/ion. Similarly, SCN¯ ion can coordinate through the
sulphur or nitrogen atom.
 Such possibilities give rise to linkage isomerism in coordination compounds. For example ;
O
M N nitrito-N
O
MO—N=O nitrito-O
M  SCN thiocyanato or thiocyanato-S
M  NCS isothiocyanato or thiocyanato-N
Note : Although ambidentate ligands have two or more donor atoms but during complex formation only one
donor atom can be used by them.

COORDINATION NUMBER P.No.: 247

 The coordination number of the central atom/ion is de- Some common co-ordination number of
termined by the number of sigma bonds between the important metals are as given below
ligands and the central atom/ion i.e. the number of Metal Coordination Metal Coordination
ligand donor atoms to which the metal is directly Number Number
attached. Pi-bonds, if any, between the ligating atom Cu +
2, 4 Ni 2+
4, 6
and the central atom/ion are not considered for the de- Ag +
2 Fe 2+
4, 6
termination of coordination number. The sigma Au + 2, 4 Fe 3+ 6
bonding electrons may be indicated by a pair of dots,
Hg 22+ 2 Co 2+ 4, 6
preceding the donor atom in the ligand formula as in :
Cu 2+ 4, 6 Co 3+ 6
[Co (: NH3)6]3+, [Fe (: CN)6]3–, [Ni (: CO)4], [Co (: Cl4)]2–. Ag 2+
4 Al 3+ 6
 Coordination number of 6 (most common), 4 (after 6) Pt 2+
4 Sc 3+
6
and 2 ( after 4) are the most common coordination num- Pd 2+ 4 Pt 4+ 6
bers and odd coordination numbers are generally not Mg 2+
6 Pd 4+
6
found (rare).
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Coordination Compounds 123

COORDINATION POLYHEDRON P.No.: 248

 The spatial arrangement of the ligand atoms which are directly attached to the central atom/ion gives a
coordination polyhedron about the central atom. Figure below shows the shapes of tetrahedral, square
planar, octahedral, square pyramidal and trigonal bipyramidal coordination polyhedra. [Co(NH3)6]3+ has an
octahedral geometry, while [PtCl4]2– and Ni(CO)4, are square planar and tetrahedral, respectively.
L
L L L
L L L
L L
L L
M M L
M M
L L L L M L
L L L
L Square planar L L L
Tetrahedral Octahedral Square pyramidal Trigonal bipyramidal
entity
entity entity entity entity

OXIDATION NUMBER OF CENTRAL ATOM P.No.: 248

 The oxidation number of the central atom is defined as the charge it would carry if all the ligands are
removed along with the electron pairs that are shared with the central atom.
 Metal oxidation number is represented by a Roman numeral in parentheses following the name of the
coordination entity. For example oxidation number of iron in [Fe(CN)6]3– is +3 and it is written as Fe(III).

HOMOLEPTIC AND HETEROLEPTIC COMPLEXES P.No.: 248

 Complexes in which a metal is bound to only one type of donor groups, e.g., [Cr(NH3)6]3+, are known as
homoleptic. Complexes in which a metal is bound to more than one type of donor groups, e.g., [Co(NH3)4Br2]+,
are known as heteroleptic.

02 17.
(3) 36 (4) 32
In the complex [Pt(py)4][PtCl4], the oxidation numbers
11. The oxidation number of Co in the complex ion of Pt atom in former and latter part of the compound
[CoCl(NH3)5]+2 is: are respectively
(1) +2 (2) +3 (1) 0 and 0 (2) +4 and +2
(3) +4 (4) +6 (3) +2 and +2 (4) 0 and +4
12. Which is a pair of ambidentate ligands among the 18. Which of the following is correct value of x in Cr(CO)x?
following? (1) 2 (2) 4
(1) CN–, NO2– (2) NO3–, NO2– (3) 6 (4) unpredictable
(3) CNS–, C2O4–2 (4) C2O4–2, SO4–2 19. The EAN of platinum in potassium hexachloroplatinate
13. What is the coordination number of Cr in K3[Cr(Ox)3] (IV) is:
(1) 6 (2) 4 (1) 86 (2) 46
(3) 3 (4) 2 (3) 36 (4) 84
14. The EAN of nickel in Ni(CO)4 is: 20. Which one is bidentate ligand?
(1) 38 (2) 36 (1) C2O4– (2) NH2.CH2.CH2.NH2
(3) 28 (4) 54 (3) None of these (4) Both (1) and (2)
15. NH2 . NH2 serves as: 21. The value of x on the [Ni(CN)4] x is:
(1) monodentate ligand (2) Both (1) and (3) (1) +2 (2) 0
(3) bridging ligand (4) chelating ligand (3) –2 (4) +4
16. What is the EAN of central metal in [Ni(gly)2] (At. No. 22. Coordination number of Ni in [Ni(C2O4)3] 4– is:
of Ni = 28) (1) 3 (2) 4
(1) 30 (2) 34 (3) 5 (4) 6
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124 Coordination Compounds

23. The oxidation state of oxygen in O2[PtF6] is (3) c, a (4) a, b

(1) zero (2) – 1/2 25. The complex that violates the EAN:
(3) +1 (4) + 1/2 (1) potassium ferrocyanide
24. Among the properties (a) reducing (b) oxidizing (c) (2) nickel carbonyl
complexing, the set of properties shown by CN– towards (3) potassium ferricyanide
metal species is: (4) cobalt (III) hexaammine chloride
(1) a, b, c (2) b, c

9.3 NOMENCLATURE OF COORDINATION COMPOUNDS P.No.: 248

9.3.1

 The following rules are followed while writing the formulas :

1. The central atom is placed first.
2. The ligands are then placed in alphabetical order. The placement of a ligand in the list does not depend
on its charge.
3. Polydentate ligands are also placed alphabetically. In case of abbreviated ligand, the first letter of the
abbreviation is used to determine the position of the ligand in the alphabetical order.
4. The formula for the entire coordination entity, whether charged or not, is enclosed in square brackets.
When ligands are polyatomic, their formulae is enclosed in parentheses. The abbreviations of the
ligands are also enclosed in parentheses.
5. There should be no space between the ligands and the metal within a coordination sphere.
6. When the formula of a charged coordination entity is to be written without that of the counter ion, the
charge is indicated outside the square brackets as a right superscript with the number before the sign.
For example, [Co(H2O)6]3+, [Fe(CN)6]3– etc.
7. The charge of the cation(s) is balanced by the charge of the anion(s).

9.3.2

 The following rules are followed when naming coordination compounds :

 Like simple salts the cation is named first in both positively and negatively charged coordination entities.
Examples : [Ag(NH3)2]Cl, diamminesilver(I) chloride. K3[Fe(CN)6], potassium hexacyanidoferrate (III).
 The ligands are named in an alphabetical order (according to the name of ligand, not the prefix) before
the name of the central atom / ion. Examples :
1. [Pt(NH3)BrCl(CH3NH2)], amminebromidochloridomethylamineplatinum(II).
2. [Co(H2O)2(ox)2]–, diaquabis(oxalato)cobaltate(III).
 Names of the anionic ligands end in – o and those of neutral ligands are the same except aqua for H2O,
ammine for NH3, carbonyl for CO, thiocarbonyl for CS and nitrosyl for NO. But names of cationic
ligands end in–ium.
Some more important examples of neutral and cationic ligands are :
tetraphosphorus — P4
dioxygen — O2
octasulphur — S8
urea — CO(NH2)2
hydrazinium — N2H5 +
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Coordination Compounds 125

 Prefixes mono, di, tri, etc., are used to indicate the number of the one 2 di bis
kind of ligands in the coordination entity. When the names of the ligands 3 tri tris
include a numerical prefix or are complicated or whenever the use of 4 tetra tetrakis
normal prefixes creates some confusion, it is set off in parentheses and
5 penta pentakis
the second set of prefixes is used.
6 hexa hexakis
7 hepta heptakis
Examples ;
1. [CoCl2(NH2CH2CH2NH2)2]+, dichloridobis(ethane-1,2-diamine)cobalt(III).
2. [NiCl2(PPh3)2], dichloridobis(triphenylphosphine)nickel(II).
 Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by Roman
numeral in the parentheses after the name of metal.
 If the complex ion is a cation, the metal is named same as the element. For example, Co in a complex
cation is called cobalt and Pt is called platinum. If the complex ion is an anion, the name of the metal
ends with the suffix - ate. For example, Co in a complex anion, [Co(SCN)4]2– is called cobaltate. For
some metals, the Latin names are used in the complex anions.
iron (Fe) ferrate lead (Pb) plumbate
silver (Ag) argentate tin (Sn) stannate
gold (Au) aurate
Examples ;
1. [Co(NH3)4Cl2]+, pentaamminechloridocobalt(III).
2. (NH4)2 [Co(SCN)4], ammonium tetrathiocyanato-S-cobaltate(II).
 The neutral complex molecule is named similar to that of the complex cation.
Example ; [CrCl3(py)3], trichloridotris(pyridine)chromium(III).
 The prefixes cis- and trans- designate adjacent and opposite geometric locations. For examples,
[Pt(NH3)2Cl2], cis- and trans-diamminedichloridoplatinum(II),
[CoCl2(NH3)4]+, cis- and trans-tetraamminedichloridocobalt(III).

cis– trans–

9.3.3
 Ist case : The name of a bridge complex is prefixed by µ–.
If the situation on both sides of the bridge is symmetrical then we can write the name of remaining complex
at one place like
5
(NH3 )5 Cr — OH — Cr(NH3 )5  Cl5
µ–hydroxidobis(pentaamminechromium(III)) chloride
OR we could also have written the name of one side of the bridge ligand and then the name of bridge ligand
and then the other side of the bridge, like
5
(NH3 )5 Cr — OH — Cr(NH3 )5  Cl5
pentaamminechromium(III)–µ–hydroxidopentaamminechromium(III) chloride
 IInd case : If the compound is unsymmetrical on both sides of the bridge then we have to follow the second
rule, i.e. write the name of one side then that of the bridge and then that of the second side, like
OH–
(H2O)4 Co Cr (NH3)4 (SO4)2
NH2
tetraaquacobalt(III)–µ–amido–µ–hydroxidotetramminechromium(III) sulphate
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126 Coordination Compounds

NCERT LIKE PROBLEM NCERT P.No.-248

Write the structural formula corresponding to each of the following IUPAC names :
(a) potassium tetracyanidozincate (II) (b) tetracarbonyl nickel (0)
(c) potassium tetracyanonickelate (0) (d) potassium tris(oxalato)aluminate (III)

(a) K2[ZnII(CN)4] (b) [Ni0(CO)4] (c) K4[Ni0(CN)4] (d) K3[AlIII(C2O4)3]

Refer IUPAC rule.

NCERT LIKE PROBLEM NCERT P.No.-248

Write IUPAC names of the following :
(a) [Cr(acac)3] (b) [V(H2O)6]Cl3 (c) (NH4)3[Co(C2O4)3](d) K2 [CrO4]

(a) tris (acetylacetonato) chromium(III)

(b) hexaaquavanadium (III) chloride
(c) ammonium tris(oxalato)cobaltate(III) or ammonium trioxalatocobaltate(III)
(d) potassium tetraoxidochromate(VI)
Refer IUPAC nomenclature rule.

03 (3) NaFe[Fe(CN)6] (4) Na2[Fe(CN)6 NO2]

32. The IUPAC name of [Co(NH3)3 (NO2)3] is
26. The IUPAC name of the coordination compound
K3[Fe(CN)6] is : (1) triamminetrinitro-N-cobalt (III)
(1) potassium hexacyanidoferrate (II) (2) trinitrotriammine cobalt (II)
(2) potassium hexacyanidoferrate (III) (3) trinitrotriammine cobalt (III) ion
(3) potassium hexacyanoiron (II) (4) trinitrotriammine cobaltate (III)
(4) tripotassium hexacyanidoiron (II) 33. The IUPAC name of K4[Fe(CN)6] 3 is
27. The IUPAC name for the complex [Co(NO2)(NH3)5]Cl2 (1) potassium hexacyanidoferrate (II)
is
(2) potassium ferrocyanide
(1) nitro-N-pentaamminecobalt (III) chloride
(3) tetrapotassium hexacyanidoferrate (II)
(2) nitro-N-pentaamminecobalt (II) chloride
(3) pentaammine nitro-N-cobalt (II) chloride (4) tetrapotassium ferroushexacyanide (II)
(4) pentaammine nitro-N-cobalt (III) chloride 34. The correct nomenclature for Fe4[Fe(CN)6] 3 is
28. Which among the following will be named as dibromido- (1) ferroso-ferric cyanide
bis-(ethylenediamine) chromium (III) bromide? (2) ferric–ferrous hexacyanate
(1) [Cr(en)3]Br3 (2) [Cr(en)2Br2]Br (3) iron (III) hexacyanidoferrate (II)
(3) [Cr(en)Br4]– (4) [Cr(en)Br2]Br
(4) hexacynoferrate (III–II)
29. The formula of the complex tris (ethylenediamine)
35. The IUPAC name of compound Na3[Co(ONO6] will be
cobalt (III) sulphate is
(1) [Co(en) 2SO4] (2) [Co(en) 3SO4] (1) hexanitritocobalt (III) sodium
(3) [Co(en)3] 2SO 4 (4) [Co(en)3] 2 (SO4)3 (2) sodium cobalt nitrite
30. The IUPAC name of the complex [Pt(NH3)2Cl2] is (3) sodium hexanitrocobaltate (III)
(1) platinum (II) diammino dichloride (4) sodium hexanitrito-o-cobaltate (III)
(2) diammine dichlorido platinum (II) 36. IUPAC name of [Co(ONO)(NH3)5Cl2] is
(3) bis (ammino) dichloro platinum (IV) (1) pentaammine nitro cobalt (III) chloride
(4) dichloro diammine platinum (II) (2) pentaammine nitrito-o-cobalt (III) chloride
31. The formula of sodium nitroprusside is (3) pentaammine nitroso cobalt (III) chloride
(1) Na4[Fe(CN)5NOS] (2) Na2[Fe(CN)5 NO] (4) pentaammine oxo-nitro cobalt (III) chloride
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Coordination Compounds 127

37. According to IUPAC nomenclat ure sodium 39. IUPAC name of K3[Al(C2O4)3] is called
nitroprusside is named as (1) potassium alumino oxalato
(1) sodium pentacyanonitrosyl ferrate (III) (2) potassium aluminium (III) trioxalate
(2) sodium nitroferricyanide (3) potassium trioxalato aluminate (III)
(3) sodium nitroferrocyanide (4) potassium trioxalato aluminate (IV)
(4) sodium pentacyanonitrosyl ferrate (II) 40. The IUPAC name of K3[Ir(C2O4)3] is
38. The proper name for K2[PtCl6] is (1) potassium trioxalato iridium (III)
(1) potassium platinum hexachloride (2) potassium trioxalato iridate (III)
(2) potassium hexachlorido platinum IV (3) potassium tris (oxalato) iridium (III)
(3) potassium hexachlorido platinate IV (4) potassium tris (oxalato) iridate (III)
(4) potassium hexachlorido platinum

9.4 ISOMERISM IN CO ORDINATION COMPOUNDS P.No.: 251

STRUCTURAL ISOMERISM
9.4.1 IONISATION ISOMERISM P.No.: 253
 This type of isomerism occurs when the counter ion in a coordination compound is itself a potential ligand
and can displace a ligand which can then become the counter ion. For example, following complexes show
ionisation isomerism.
[Co(NH3)5SO4]NO3 and [Co(NH3)5NO3]SO4
[Co(NH3)4(NO2)Cl]Cl and [Co(NH3)4Cl2]NO2.
[Co(NH3)4(H2O)Cl]Br2 and [Co(NH3)4BrCl]Br.H2O. [Also an example of hydrate isomers.]
[Pt(NH3)4Cl2]Br2 and [Pt(NH3)4Br2]Cl2.
[CoCl(en)2(NO2)]SCN, [Co(en)2(NO2)SCN]Cl and [Co(en)2(SCN)Cl]NO2

9.4.2 SOLVATE / HYDRATE ISOMERISM P.No.: 254

 It occurs when water forms a part of the coordination entity or is outside it.
 This is similar to ionisation isomerism. Solvate isomers differ by whether or not a solvent molecule is
directly bonded to the metal ion or merely present as free solvent molecules in the crystal lattice. For
example, CrCl3 . 6H2O exists in three distinct isomeric forms : [Cr(H2O)6]Cl3, violet ; [CrCl(H2O)5]Cl2.H2O,
blue green : [CrCl2(H2O)4]Cl.2H2O, dark green. These three cationic isomers can be separated by cation ion
exchange from commercial CrCl3.6H2O. A fourth isomer [Cr(H2O)3Cl3], yellow green also occurs at high
concentration of HCl.
 Apart from their distinctive colours, the three isomers can be identified by the addition of excess of aqueous
silver nitrate to their aqueous solutions, which precipitates chloride in the molar ratio of 3 : 2 : 1 respectively.
Complex Reaction with AgNO3 Reaction with conc. H2SO4 (dehydrating agent)
[Cr(H2O)6]Cl3 in the molar ratio of 3 : 1 No water molecule is lost or no reaction
[CrCl(H2O)5]Cl2.H2O in the molar ratio of 2 : 1 one mole of water is lost per mole of complex
[CrCl2(H2O)4]Cl2.H2O in the molar ratio of 1 : 1 two mole of water are lost per mole of complex
Other examples are :
[Co(NH3)4(H2O)Cl]Cl2 and [Co(NH3)4Cl2]Cl.H2O
[Co(NH3)5(H2O)](NO3)3 and [Co(NH3)5(NO3)](NO3)2.H2O.

9.4.3 LINKAGE ISOMERISM P.No.: 253

 In some ligands, like ambidentate ligands, there are two possible coordination sites. In such cases, linkage
isomerism exist. e.g., NO2 group can be bonded to metal ions through nitrogen (– NO2) or through oxygen
(– ONO). SCN too can be bonded through sulphur (– SCN) thiocyanate or through nitrogen (– NCS)
isothiocyanate. For example : [Co(ONO)(NH3)5] Cl2 and [Co(NO2) (NH3)5] Cl2.
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128 Coordination Compounds

9.4.4 COORDINATION ISOMERISM P.No.: 253

 Coordination compounds made up of cationic and anionic coordination entities show this type of isomer-
ism due to the interchange of ligands between the cation and anion entities. Some of the examples are :
1. [Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
2. [Cu(NH3)4][PtCl4] and [Pt(NH3)4][CuCl4]
3. [Co(NH3)6][Cr(SCN)6] and [Cr(NH3)4(SCN)2][Co(NH3)2(SCN)4]
4. [Pt(NH3)4][PtCl6] and [Pt(NH3)4Cl2][PtCl4]
Such isomers are expected to have significant differences in their physical and chemical properties.

STEREOISOMERISM P.No.: 251

 The isomers in which atoms are bonded to each other in the same order but that differ in the arrangement of
these atoms in the space are called as stereoisomers and the phenomenon as stereoisomerism.

9.4.5 GEOMETRICAL ISOMERISM

This type of isomerism arises in heteroleptic complexes due to different possible geometric arrangements
of theligands. Geometrical isomerism is common among coordination compounds with coordination
numbers 4 and 6.
 Coordination Number Four :
1. Tetrahedral Complex : The tetrahedral compounds can not show geometrical isomerism as we all
know that all four positions are equivalent in tetrahedral geometry.
2. Square Planar Complex : In a square planar complex of
Cl NH3 Cl NH3
formula [Ma2b2] [a and b are unidentate], the two ligands
‘a’ may be arranged adjacent to each other in a cis isomer, Pt Pt
or opposite to each other in a trans isomer as depicted. Cl NH3 NH3 Cl
cis– trans–
Geometrical isomers (cis and trans) of Pt(NH3)2Cl2.
Square planar complex of the type Ma 2bc (where a, b, c are unidentates) shows two geometrical
isomers.
a b a c

M M

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

M M M

d c c b c d
aTc aTb aTd
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 A A A B
AB are unsymmetrical bidentates) shows two geo-
metrical isomers. Example is [Pt(gly)2] in which gly M M
is unsymmetrical ligand.
B B B A
Similarly, M(AB)(CD) also shows two geometrical cis– trans–
isomers.
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Coordination Compounds 129

Note : M(AA) 2, (where AA are symmetrical bidentates) 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.
+ +
Cl Cl
NH3 Cl NH 3 NH3
Co Co
NH3 NH3 NH3 NH3
NH3 Cl
cis– trans–
Geometrical isomers (cis and trans) of [Co(NH3)4Cl2]+
Number of possible isomers and the spatial arrangements of the ligands around the central metal ion for the
specific complexes are given below.
 Complexes containing only unidentate ligands Unsymmetrical bidentate ligands also show fac-
1. Ma2b4 – 2 (aa)(bb)(bb) mer isomerism.
(ab)(ab)(bb) 4. Ma3b2c – 3 (aa)(ab)(bc)
2. Ma4bc – 2 (aa)(aa)(bc) (aa)(bb)(ac)
(aa)(ab)(ac) (ab)(ab)(ac)
3. Ma3b3
5. Ma3bcd – 4 (aa)(ab)(cd)
Complexes of the formula Ma3b3, where a
(aa)(ac)(bd)
and b are monodentate ligands, may show
(aa)(ad)(bc)
two isomeric forms called fac– and mer–.
(ab)(ac)(ad)
Facial isomers have three identical ligands
on one triangular face where as meridional 6. Ma2b2c 2 – 5 (aa)(bb)(cc)
isomers have three identical ligands in a (aa)(bc)(bc)
plane bisecting the molecule. Similar isomers (bb)(ac)(ac)
are possible with some chelating ligands. (cc)(ab)(ab)
NH3 NH3 (ab)(ac)(bc)
O2N NH 3 H3 N NO2
Co Co 7. Ma2b2cd – 6
O2N NH 3 O2 N NO2
NO2 NH3 8. Ma2bcde– 9
fac– mer– 9. Mabcdef, [Pt(py)(NH3)(NO2)(Cl)(Br)(I)]– 15
The facial(fac) and meridional(mer) Note : Ma6 and Ma5b have only one form.
isomers of [Co(NH3)3(NO2)3].

 Compounds containing bidentate ligand and 2. M(AA)a2b2 – Three geometrical isomers are
unidentate ligands possible.
1. M(AA)a3b – Two geometrical isomers are a a b
possible. A b A a A a
b a
A a A a M M M

M M A b A b A a

A A a b b
a b aTa aTb bTb
a a Note : With [M(AA)b4], only one form is pos-
bTa aTa sible. M(AA)abcd have six geometrical isomers.
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130 Coordination Compounds

3. M(AA)2a2 – Two geometrical isomers are possible.
Cl Cl
Cl
en Co en Co en

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

NCERT LIKE PROBLEM NCERT P.No.-251

Draw stereoisomer of the compound [PtCl2(NH3)(OH2)] ?

Ma2bc have cis- and trans isomers.

48. Out of the following which will not show geometrical

04 isomerism?
41. The total number of possible isomers of the complex (1) [Pt(NH3)2Cl2] (2) [Co(en)2Cl2]Cl
compound [Cu 11(NH3)4] [Pt11Cl4] is (3) [Co(NH3)3Cl3] (4) [Cr(NH3)4Cl2]Cl
(1) 3 (2) 6 49. [Co(NH3)4Cl2]Cl exhibits
(3) 5 (4) 4 (1) optical isomers
42. The number of isomers possible for square planar (2) ionisation isomerism
complex K2(PdClBr2SCN] is: (3) linkage isomerism
(1) 2 (2) 4 (4) geometrical isomerism
(3) 3 (4) 6 50. The type of isomerism present in nitro pentaammino
43. [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br are the examples chromium (III) chloride is:
of: (1) Optical (2) Linkage
(1) linkage isomerism (3) Ionisation (4) Polymerisation
(2) geometrical isomerism 51. The most stable ion is:
(3) optical isomerism (1) [Fe(C2O4)3] 2– (2) [Fe(Cl)6]3–
(4) ionization isomerism (3) [Fe(CN)6] 3–
(4) [Fe(H2O)6] 3+
44. Geometrical isomerism is found in coordination 52. Which one o f the following compl ex ions has
compounds having coordination number: geometrical isomers?
(1) 6 (2) 3 (1) [Co(en)3] 3+ (2) [Ni(NH3)5Br]+
(3) 4 (tetrahedral) (4) 2 (3) [Co(NH3)2(en)2] 3+ (4) [Cr(NH3)4(en)] 3+
45. The type of isomerism shown by [Co(en)2(NCS)2]Cl and 53. Which of the following pairs represents linkage
[Co(en)2(NCS)Cl]NCS is: isomers?
(1) ionization (1) [Cu(NH3)4] [PtCl4] and [Pt(NH3)4] [CuCl4]
(2) coordination (2) [Pd(PPh3)2 (NCS)2 and [Pd(PPh3)2(SCN)2]
(3) linkage (3) [Co(NH3)5] NO3SO4 and [Co(NH3)5SO4]NO3
(4) all of these (4) [PtCl2(NH3)4]Br and [PtBr2(NH3)4Cl2
46. Which one of the following square planar complexes 54. The number of geometrical isomers of [Co(NH3)3(NO3)3]
will form two geometrical isomers? are:
(1) M A 4 (2) MA 3 B (1) 0 (2) 2
(3) MAB 3 (4) MA 2B 2 (3) 3 (4) 4
47. The square planar complex (MABCD) can show 55. A square planar complex is represented as:
(1) two optical isomers (1) Geometrical isomers
(2) three geometrical isomers (2) Optical isomerism
(3) two geometrical isomers (3) Linkage isomerism
(4) three optical isomers (4) None
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Coordination Compounds 131

9.4.6 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).
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.
en en
3+ 3+
en Co Co en

en en
dextro mirror laevo
d and l of [Co(en)3]3+
 Cis-isomer of [PtCl2(en)2]2+ show optical isomerism as shown below because of the absence of plane of
symmetry as well as centre of symmetry.
2+ 2+
Cl Cl Cl
Cl
en Pt Pt en

en en
dextro mirror laevo
d and l of cis-[PtCl2(en)2]2+
 But trans isomer of [PtCl2(en)2]2+ does not show optical isomerism.

 cis-[Co(NH3)2Cl2(en)]+ can show optical isomerism due to the absence of plane of symmetry as well as
centre of symmetry.
+ +
Cl Cl Cl
Cl
en Co3+ Co3+ en

NH3 NH 3 NH3 NH
3

dextro mirror laevo

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132 Coordination Compounds

TETRAHEDRAL COMPLEX :
 Optical isomerism is expected in tetrahedral (i) For example [As(III)(CH )(C H )(S)(C H COO)]2+,
3 2 5 6 4
complexes of the type [Mabcd] analogous to tet- shows optical isomerism as given below.
rahedral carbon atom.
a a 2+ 2+
S S

M M As As
d b b d H3 C C 2H 5 H 5C2 CH3

–
c c C6H4COO– C 6H 4COO
Mirror plane Mirror plane

 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.

05 Cl CH = CH Cl Cl

56. Which of the following is not optically active? (1) Pt (2) Pt

(1) [Co(en)3] 3+ (2) [Cr(ox)3]3– Cl Cl Cl Cl
+
(3) cis-[CoCl2(en)2] (4) trans-[CoCl 2(en) 2] + H3N Cl H3N Cl
57. Which of the following types of octahedral complexes
does not show optical isomerism? (3) Pt (4) Pt
(1) MA 2X 2Y 2 (2) [Pt(NH)3)4]2+ H3N Cl Cl NH3
n+
(3) [M(AA) 3] (4) [M(AA) 2X 2] n+ 62. [Co(en)3] 3+ ion is expected to show
58. Type of isomerism which is shown by [PtCl 2Br 2] 2– is (1) two optically active isomers: d and l forms
also observed in: (2) d, l and meso forms
(1) (CoCl2Br2] 2– (2) [Co(en)3] 3+ (3) four optically active isomers: cis, d and l isomers
(3) [PtCl4Br2] 2– (4) [PtCl3 (NO2)] 2– and trans d and l isomers
59. Which of the following statements is not true about (4) none of these
the complex ion [Pt(en)2Cl2] 2+? 63. In which case racemic mixture is obtained on mixing its
(1) It has two geometrical isomers: cis and trans. mirror images in 1:1 molar ratio?
(2) Both the cis and trans isomers display optical (1) Cr(en)3] 3+
activity.
(2) [Ni(DMG)2]
(3) Only the cis isomer displays optical activity.
(3) cis-[Cu(Gly)2]
(4) Only the cis isomer has non-superimposable
(4) All the three
mirror image
64. The complex that exists as a pair of enantiomers is
60. Tris (ethylenediamine) cobalt (III) cation, [Co(en)3] 3+,
can have (1) trans-[Co(H2NCH2 CH2 CNH2)2Cl2] +
(1) three stereoisomers, all chiral and optically active (2) [Co(H2 NCH2 CH2 NH2)3] 3+
(2) two chiral stereo isomers (enantiomers) and one (3) [Pt(PPh3) (Cl) (Br) (CH3)] –
achiral (4) cis–[CoNH3)4Cl2]+
(3) three stereoisomers, all achiral 65. Which one of the following has largest number of
(4) two stereoisomers, both achiral isomers?
61. Which of the following is considered to be an (1) [Co(en)2Cl2]+ (2) [Co(NH3)5Cl]2+
2+
anticancer species? (3) [Ir(PR3)2H(CO)] (4) [Ru(NH3)4Cl2]+
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Coordination Compounds 133

66. Which of the following complexes exhibit optical
isomerism? A
(1) Trans-tetraamminedithiocyanatochromium (III) F B
ion M
(2) Cis-diamminedicarbonatocobaltate (III) ion E C
(3) Trans-diamminedicarbonatocobaltate (I) ion D
(4) Cis-bis (glycinato) platinum (II)
(1) optical isomerism only
67. Which of the following will show optical isomerism?
(2) both optical and geometrical isomerism
(1) [Cu(NH3)4]2+ (2) [ZnCl4] 2–
3–
(3) geometrical isomerism only
(3) [Cr(C2O4)3] (4) [Co(CN)6]3–
(4) none of the above
68. Which of the following complex species is not expected
70. Which of the following has on optical isomer? (en =
to exhibit optical isomerism?
ethylenediamine)?
(1) Co(en)3Cl2]+ (2) [Co(en)2 Cl2]+
(1) [Zn(en)(NH3)2] 2+ (2) [Co(en)3] 3+
(3) [Co(NH3)3Cl3] (4) [Co(en)(NH3)Cl2]+ 3+
(3) [Co(H2O) 4(en)] (4) [Zn(en) 2] 2+
69. The complex shown below can exhibit

9.5 BONDING IN COORDINATION COMPOUNDS P.No.: 254

 Alfred-Werner described the bonding characteristic in coordination compounds. But this theory failed to
explain certain basic questions like :
1. Why only certain elements possess the remarkable property of forming compounds?
2. Why the bonds in coordination compounds have directional properties?
3. Why coordination compounds have the characteristic magnetic and optical properties?
Many theories/approaches have been put forward to explain the nature of bonding in coordination
compounds; these are valence bond theory (VBT), crystal field theory (CFT), ligand field theory (LFT) and
molecular orbital theory (MOT).

9.5.1 P.No.: 254

 The valence bond theory, VBT, was extended to coordination compounds by Linus Pauling in 1931.
 The formation of a complex involves reaction between a lewis base (ligand) and a lewis acid (metal or
metal ion) with the formation of a coordinate-covalent (or dative) bonds between them.
 The model utilizes hybridisation of (n – 1) d, ns, np or ns, np, nd orbitals of metal atom or ion to yield a set
of equivalent orbitals of definite geometry to account for the observed structures such as octahedral, square
planar and tetrahedral, and magnetic properties of complexes. The number of unpaired electrons, measured
by the magnetic moment of the compounds determines which d-orbitals are used.
 These hybrid orbitals are allowed to overlap with ligand orbitals that can donate electron pairs for bonding.
Following table provides the types of hybridisation with different coordination number.
Coordination number of metal Type of hybridisation Shape of complex
3
4 sp Tetrahedral
4 dsp2 Square planer
5 sp3d Trigonal bipyramidal
6 3 2 Octahedral
sp d
6 d2sp3 Octahedral
 It is to be noted that the type of hybridisation of metal and shape of complex involved can be predicted
conveniently, if some characteristic of the complex like magnetic nature, geometry or whether exhibits
isomerism or not, etc., be known.
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134 Coordination Compounds

BONDING IN COMPOUNDS WITH COORDINATION NUMBER SIX P.No.: 254

 In the diamagnetic octahedral complex, [Co(NH3)6]3+, the cobalt ion is in +3 oxidation state and has the
electronic configuration represented as shown below.
4s 4p
Co3+,[Ar]3d6

[Co(NH3)6]3+

(inner orbital or d2sp3 hybrid orbital

low spin complex) Six pairs of electrons from six NH3 molecules.
 Thus, the complex has octahedral geometry and is diamagnetic because of the absence of unpaired electron.
Since in the formation of complex the inner d-orbital (3d) is used in hybridisation, the complex is called an
inner orbital or low spin or spin paired complex.
 The complex [FeF6]4– is paramagnetic and uses outer orbital (4d) in hybridisation (sp3d2) ; it is thus called
as outer orbital or high spin or spin free complex. So,
3d 4s 4p 4d
Fe2+, [Ar]3d6

[FeF6]4–
sp3d2 hybrid orbitals
Six pairs of electrons from six F– ions.

BONDING IN COMPOUNDS WITH COORDINATION NUMBER FOUR

 In the paramagnetic and tetrahedral complex [NiCl4]2–, the nickel is in +2 oxidation state and the ion has
the electronic configuration 3d8. The hybridisation scheme is as shown in figure.
3d 4s 4p
2+ 8
Ni , [Ar]3d

[NiCl4]2–

sp3 hybrid orbitals

Four pairs of electrons from four Cl– ions.
 The compound is paramagnetic since it contains two unpaired electrons.
 Similarly complex [Ni(CO) 4] has tetrahedral geometry and is diamagnetic as it contains no unpaired
electrons. The hybridisation scheme is as shown in figure.
3d 4s 4p
Ni0, [Ar] 3d8 4s2

[Ni(CO)4]
sp3 hybrid orbitals
Four pairs of electrons from four CO molecules.
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Coordination Compounds 135

 Complexes of Pd(II) and Pt (II) are usually four-coordinate, square planar, and diamagnetic and this
arrangement is often found for Ni(II) complexes as well, e.g., in [Ni(CN)4]2– (here nickel is in +2 oxidation
state and has electronic configuration 3d8). In as much as the free ion is in the ground state each case is
paramagnetic, the bonding picture has to include pairing of electrons as well as ligand-metal-ligand bond
angles of 90° and this occurs via hybridisation of one (n – 1) d, one ns and two np orbitals to form four
equivalent dsp2 hybrid orbitals directed toward the corners of a square. These orbitals then participate in
covalent coordinate s bonds with the ligands, the bonding electron pairs being furnished by the ligands. The
hybridisation scheme for [PtCl4]2– is as shown in figure.
5d 6s 6p
Pt2+, [Xe]4f14 5d8

[PtCl4]2–
dsp2 hybrid orbitals
Four pairs of electrons from four Cl– ions.
Similarly the hybridisation scheme for [Ni(CN)4]2– is as shown in figure.
3d 4s 4p
Ni2+, [Ar]3d8

[Ni(CN)4]2–
dsp2 hybrid orbitals
Four pairs of electrons from four CN– ions.
 It is found that [Cu(NH3)4]2+ is square planar and paramagnetic with one unpaired electron in 4p-orbital.
The hybridisation scheme is as follow.
3d 4s 4p
Cu2+, [Ar]3d9

[Cu(NH3)4]2+
dsp2 hybrid orbitals
Four pairs of electrons from four NH3 molecules.
3–
Note : [Ni(CN)5] is found to be diamagnetic with 2 types of Ni – C bond lengths, out of which four bond
lengths are found to be equal and the fifth one is different. The hybridisation scheme for [Ni(CN)5]3– is as
shown in figure.
3d 4s 4p
2+ 8
Ni , [Ar]3d

[Ni(CN)5]3–
dsp3 hybrid orbitals
Five lone pairs of electrons from five CN – ions.

CN
CN CN
Ni square pyramidal.

CN CN
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136 Coordination Compounds

9.5.2 P.No.: 256

 Additional information for understanding the nature of coordination entities is provided by magnetic sus-
ceptibility measurements.
 We have noted that coordination compounds generally have partially filled d orbitals and as such they are
expected to show characteristic magnetic properties depending upon the oxidation state, electron configu-
ration, coordination number of the central metal and the nature of the ligand field.
 It is experimentally possible to determine the magnetic moments of coordination compounds which can be
utilized for understanding the structures of these compounds.
 The number of unpaired electrons in any complex can be easily calculated from the configuration of the
metal ion, its coordination number and the nature of the ligands involved( strong or weak from the spectro-
chemical series) and after that the magnetic moment of the complexes can be easily calculated using ;

Magnetic Moment = n( n  2) Bohr Magneton ; n = number of unpaired electrons

For metal ions with upto three electrons in the d-orbitals like Ti3+, (d1) ; V3+ (d2) ; Cr3+ (d3) ; two vacant d-
orbitals are easily available for octahedral hybridisation. The magnetic behaviour of these free ions and
their coordination entities is similar. When more than three 3d electrons are present, like in Cr2+ and Mn3+
(d4) ; Mn2+ and Fe3+ (d5) ; Fe2+ and Co3+ (d6) ; the required two vacant orbitals for hybridisation is not
directly available (as a consequence of Hund’s rules). Thus, for d4, d5 and d6 cases, two vacant d-orbitals are
only available for hybridisation as a result of pairing of 3d electrons which leaves two, one and zero
unpaired electrons respectively.
 The magnetic data agree with maximum spin pairing in many cases, especially with coordination compounds
containing d6 ion. However, there are complications with the coordination compounds / species having d4
and d5 ions.
[Mn(CN) 6] 3– has a magnetic moment equal to two unpaired electrons while [MnCl 6] 3– has a magnetic
moment equal to four unpaired electrons.
 Similarly [Fe(CN)6]3– has magnetic moment of a single unpaired electron while [FeF6]3– has a magnetic
moment of five unpaired electrons. [CoF6]3– is paramagnetic with four unpaired electrons while [Co(C2O4)]3–
is diamagnetic.
This anomalous behaviour is explained by valence bond theory in terms of formation of inner orbitals and
outer orbitals complexes.
 [Mn(CN)6]3– , [Fe(CN)6]3– and [Co(C2O4)2]3– are inner orbital complexes involving d2sp3 hybridisation, the
former two are paramagnetic and the latter diamagnetic. [MnCl6]3–, [FeF6]3– and [CoF6]3– are outer orbital
complexes involving sp3d2 hybridisation and are paramagnetic having four, five and four electrons respectively.

9.5.3 P.No.: 257

 While the valence bond theory, to a large extent, explains the formation, structures and magnetic behaviour
of coordination compounds, it suffers from the following shortcomings :
1. A number of assumptions are involved.
2. There is no quantitative interpretation of magnetic data.
3. It has nothing to say about the spectral (colour) properties of coordination compounds.
4. It does not give a quantitative interpretation of the thermodynamic or kinetic stabilities of coordina-
tion compounds.
5. It does not make exact predictions regarding the tetrahedral and square-planar structures of 4-coordi-
nate complexes.
6. It does not distinguish between strong and weak ligands.
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Coordination Compounds 137

81. Consider the following complex ions, P, Q, and R.
06 P = [FeF6] 3–, Q = [V(H2O)6] 2+ and R = [Fe(H2O)6] 2+, the
71. The hybridization of Fe in K4[Fe(CN)6] complex is: correct order of the complex ions, according to their
spin only magnetic moment values (in B. M.) is:
(1) d 2sp 2 (2) dsp 2
2 3
(1) Q<R<P (2) R<Q<P
(3) d sp (4) sp 3
(3) R<P<Q (4) Q<P<R
72. The structure of iron pentacarbonyl is:
82. Among the following ions which one has the highest
(1) square planar
paramagnetism?
(2) triangular
(1) [Cr(H2O)6]3+ (2) [Cu(H2O)6)2+
(3) trigonal bipyramidal
(3) [Fe(H2O)6] 2+ (4) [Zn(H2O) 6] 2+
(4) none of these
83. The reaction [Fe(CNS)6]  [FeF6] 3– takes place with:
3–
3+
73. [Cr(NH3)6] ion is:
(1) decrease in magnetic moment
(1) diamagnetic (2) square planar
(2) increase in coordination number
(3) paramagnetic (4) none of these
(3) decrease in coordination number
74. In hexacyanomanganate (II) ion the d2sp2-hybrid state.
(4) increase in magnetic moment
The number of unpaired electrons in the complex is:
84. dsp2-hybridization is found in
(1) 2 (2) 3
(1) [Co(NH3)2]2+ (2) [NiCl4)] 2–
(3) 0 (4) 1
(3) [Co(NH3)6]3+ (4) [Ni(CN4)] 2–
75. Which is true in the case of [Ni(CO)4] complex?
85. The primary valency of iron in K4[Fe(CN)6] is
(1) All are correct
(1) 1 (2) 3
(2) Tetrahedral shape of the molecule
(3) 2 (4) 4
(3) Hybridization of Ni is sp3
86. The magnetic moment of K4[Fe(CN)6] is found to be 17
(4) Diamagnetic
BM. How many unpaired electron(s) is/are present per
76. Which one of the following is an inner orbital complex molecule?
as well as diamagnetic in nature?
(1) 2 (2) 3
(1) [Co(NH3)6]3+ (2) [Cr(NH3)6]3+
(3) 4 (4) 1
(3) [Ni(NH3)6]2+ (4) [Zn(NH3)6] 2+
87. Cr(H2O)6]Cl3 has a magnetic moment of 3.83 B.M. The
77. Which of the following complex exhibits the highest correct distribution of 3d electrons in the chromium of
paramagnetic behaviour? the complex is
(1) [Ti(NH3)6]3+ (1) 3dxy1, 3dyz1, 3dz2
(2) [Fe(en)(bpy)(NH 3) 2] 2+ (2) 3d1xy, 3d1yz, 3d1zx
–
(3) [Co(OX)2(OH)2] (3) 3d(x2 – y2)1, 3d1z2, 3d1xz
+
(4) [V(gly)2(OH)2(NH3)2] (4) 3dxy1, 3d1(x2 – y2), 3d1y2
78. A magnetic moment of 1.73 B.M. will be shown by one 88. Which of the following complex is an outer orbital
among the following:
(1) [Ni(NH3)6]2+ (2) [Mn(CN)6] 4–
2+ 2–
(1) [Cu(NH3)4] (2) [Ni(CN)4]
(3) [Co(NH3)6]3+ (4) [Fe(CN)6] 4–
(3) TiCl4 (4) [CoCl6]4–
89. The correct order of magnetic moments (spin values in
79. A square planar complex is followed by hybridization B.M.) among is:
of which atomic orbitals?
(1) [Fe(CN)6] 4– > [CoCl4] 2– > [MnCl4] 2–
(1) s, p x, py, dyz (2) s, px, py, dz2
(2) [CoCl4]2– > [Fe(CN)6]4– > [CoCl4] 2–
(3) s, p x, py, d x2 – y2 (4) s, px, py, dxy
(3) [Fe(CN)6] 4– > [MnCl4] 2– > [CoCl4] 2–
80. Among the following complexes (K to P),
(4) [MnCl4] 2– > [CoCl4] 2– > [Fe(CN)6] 4–
K3[Fe(CN)6](K), [Co(NH3)6]Cl3 (L),
(Atomic no. of Mn = 25, Fe = 26, Co = 27)
Na3[Co(oxalate)3] (M), [Ni(H2O)6]Cl2 (N),
90. Which one of the following has the regular tetrahedral
K2[Pt(CN)4] (O), and [Zn(H2O)6](NO3)2 (P)
structure?
The diamagnetic complexes are:
(1) [Ni(CN)4]2– (2) SF 4
(1) K, L, M, N (2) L, M, O, P –
(3) BF4 (4) XeF4
(3) K, M, O, P (4) L, M, N, O
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138 Coordination Compounds

9.5.4

 The drawbacks of VBT of coordination compounds are, to a considerable extent, removed by the Crystal
Field Theory.
 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.
 Ligands are treated as point charges in case of anions or dipoles in case of neutral molecules. 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.
CRYSTAL FIELD SPLITTING IN OCTAHEDRAL COORDINATION ENTITIES P.No.: 257

 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.
 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 d x  y and d z orbitals (axial orbitals) which point towards the axis along the direction
2 2 2

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.
 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.
 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 0 (the subscript o is for octahedral). Thus,
the energy of the two eg orbitals will increase by (3/5)0 and that of the three t2g will decrease by (2/5) 0.
Z
Energy Y Energy correspond
dx 2
 y2
, dz 2

eg to absorption.
3/5 0 or + 0.6 0 average
X + 6L 0 energy (Bari center)
2/5 0 or – 0.4 0
Metal Average energy level
of 'd ' orbitals in spherical t2g
d orbitals dxy, dxz , dyz
crystal field Energy corresponds to
Crystal field splitting evolution of energy.
for octahedral complex
Free metal ion
Figure showing crystal field splitting in octahedral complex.
 The crystal field splitting, 0, 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– < Cl– < NO3– < F– < OH– < EtOH < C2O42– < H2O < NCS– < EDTA < NH3 < en < NO2– < CN–
< CO
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, 0 and the pairing energy, P (P represents the energy required for electron pairing
in a single orbital). The two possibilites are :
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Coordination Compounds 139

1. If 0 < P, the fourth electron enters one of the eg orbitals giving the configuration t32geg1. Ligands for
which 0 < P are known as weak field ligands and form high spin complexes.
2. If 0 > P, it becomes more energetically favourable for the fourth electron to occupy a t2g orbital with
configuration t2g4 eg0. Ligands which produce this effect are known as strong field ligands and form low
spin complexes.

CALCULATION OF CRYSTAL FIELD STABILISATION ENERGY (CGSE)

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

where n and n are number of electron(s) in t2g and 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.

CRYSTAL FIELD SPLITTING IN TETRAHEDRAL COORDINATION ENTITIES P.No.: 259

 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.
1. There are only four ligands instead of six, so the ligand field is only two thirds the size ; as the ligand
field spliting is also the two thirds the size and
2. The direction of the orbitals does not concide with the direction of the ligands. This reduces the
2 2 4
crystal field spliting by roughly further two third. So  t     0 .
3 3 9
Consequently, the orbital splitting energies are not sufficiently large for forcing pairing and, therefore, low
spin configurations are rarely observed.

Figure showing crystal field splitting in tetrahedral complex.

 Since t < 0 crystal field spliting favours the formation of octahedral complexes.
 sp = 1.3 0.

9.5.5 COLOUR IN COORDINATION COMPOUNDS P.No.: 259

 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.
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140 Coordination Compounds

 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 t2g 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
(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.
Relationship between the wavelength of light absorbed and the colour observed In some coordination entitles
Coordination entity Wavelength of light Colour of light Colour of coordination
absorbed (nm) absorbed entity
[CoCl(NH3)5]2+ 535 Yellow Violet
[Co(NH3)5(H2O)]3+ 500 Blue Green Red
[Co(NH3)6]3+ 475 Blue Yellow Orange
[Co(CN)6]3– 310 Ultraviolet Pale Yellow
[Cu(H2O)4]2+ 600 Red Blue
[Ti(H2O)6]3+ 498 Blue Green Purple
Note :
1. 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.
2. 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], the colour change is observed when ethyl-
enediamine is progressively added to it.
Molar ratio of en : Ni Coloured observed
1 :1 Pale blue
2 :1 Blue / Purple
3 :1 Violet
3+ 3
Note : Ruby is Al2O3 in which 0.5 – 1% Cr ions (d electron system) are randomly distributed in the
positions normally occupied by Al3+. We may consider Cr(III) species as octahedral Cr(III) complexes
incorporated into the alumina lattice ; d - d transition of electron at these centres/points give rise to the
colour (red).
Emerland is the mineral beryl (Be3Al2Si6O18) in which Cr3+ ions occupy octahedral sites, but in this
case low energy corresponding to yellow red and blue is absorbed and light corresponding to green
region is transmitted.

9.5.6 LIMITATIONS OF CRYSTAL FIELD THEORY PAGE P.No.: 261

 It considers only the metal ion d-orbitals and gives no consideration at all to other metal orbitals (such as s,
px, py and pz orbitals).
 It is unable to account satisfactorily for the relative strengths of ligands. For example it gives no explana-
tion as to why H2O is a stronger ligand than OH– in the spectrochemical series.
 According to this theory, the bond between the metal and ligands are purely ionic. It gives no account on
the partly covalent nature of the metal ligand bonds.
 The CFT cannot account for the -bonding in complexes.
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Coordination Compounds 141

07 98. Which of the following is -acid ligand?

(1) NH 3 (2) CO
91. If the crystal filed splitting energy for octahedral (3) F –
(4) ethylene diamine
complexes is 0 and for tetrahedral complexes is t, the
two are related as 99. In the complex ion MLn6 , Mn+ has five d-electrons and
L is a weak field ligand. According to crystal field theory,
4 1 the magnetic properties of the complex ion correspond
(1) t =  0 (2) t =  0
9 2 to how many unpaired electrons?
1 4 (1) 0 (2) 5
(3) 0 = t (4) 0 = t
2 9 (3) 2 (4) 3
92. Which is the strongest field ligand? 100. Increasing order of 0 of the following complex is
(1) NO 2– (2) CN – (1) Cr(NH3)63+ < Cr(H2O)63+ < Cr(NO2)63–
(3) NH 3 (4) En (2) Cr(H2O)63+ > Cr(NH3)63+ > Cr(NO2)63–
93. Considering H2O as a weak field ligand, the number of (3) Cr(H2O)63+ < Cr(NH3)63+ < Cr(NO2)63–
unpaired electrons in Mn(H 2O)62  will be: (4) Cr(NH3)63+ < Cr(NO2)63– < Cr(H2O)63+

(1) 3 (2) 2 101. The val ue of  0 for RhCl 6 3– is 243 kJ /mol what
wavelength of light will promote an electron from. The
(3) 5 (4) 4 colour of the complex is
94. Which of the following complex ions is expected to
(1) Blue (2) Green
absorb visible light?
(3) Yellow (4) Orange
(1) [Zn(NH3)6] 2+ (2) [Cr(NH3)6]3+
6 2
102. For the t e system, the value of magnetic moment
(3) [Ti(en)2NH3)2] 4+ (4) [Sc(H2O)3(NH3)3] 3+ 2g g
(µ) is:
95. Which of the following statements are correct?
(1) 2.83 B.M. (2) 1.73 B.M.
(i) In octahedral complexes, dz2, dx2 – y2 orbitals have
higher energy than d xy, dyz and d zx orbitals. (3) 3.87 B.M. (4) 4.92 B.M.
(ii) In tetrahedral complexes d xy, d yz and d zx orbitals 103. Which of the following system has maximum number
have higher energy than dz2, dx2 – y2 orbitals. of unpaired electrons?
(iii) The colours of complexes are due to electronic (1) d5 (octahedral)
transitions from one set of d–orbitals to another (2) d9 (octahedral)
set of orbitals.
(3) d7 (octahedral)
9 (4) d6 (octahedral)
(iv) tedrahedral = , octahedral
4 104. Which ion produces a small crystal field splitting (a
(1) (i), (ii) and (iii) (2) (i) and (iv) weak ligand field)?
(3) (iii) and (iv) (4) (ii), (iii) and (iv) (1) I– (2) Cl–
–
96. In crystal field splitting for a tetrahedral complex, the (3) F (4) All
number of orbitals pushed down in energy are 105. Which of the following pairs is not correctly matched?
(1) 3 (2) zero (1) Effective atomic number of Pt in [PtCl6] 2– = 84
(3) 5 (4) 2 (2) Absorption peak for [Cr III (NH 3 ) 6 ] 3+ = 21680
97. Among the ligands NH3, en, CN– and CO, the correct cm–1
order of their increasing field strength, is
(3) Crystal field stabilization energy of d 2 in weak
(1) CO < NH3 < en < CN– ligand field = (–)0.8 0
(2) NH3 < en < CN– < CO (4) Example of weak ligand field for d5 configuration
(3) CN– < NH3 < CO < en = [MnII F6] –4
(4) en < CN– < NH3 < CO
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142 Coordination Compounds

9.7 STABILITY OF COORDINATION COMPOUNDS P.No.: 261

 The stability of a coordination compound [MLn] is measured in terms of the stability constant (equilibrium
constant) given by the expression,
 n = [MLn] / [M(H2O)n][L]n
For the overall reaction :
M(H2O)n + nL   ML + nH O
n 2
By convention, the water displaced is ignored, as its concentration remains essentially constant. The above
overall reaction takes place in steps, with a stability (formation) constant, K1, K2, K3, ...... Kn for each step
as represented below :
 ML(H O) + H O ; K = [ML(H O) ] / {[M(H O) ][L]}
M(H2O)n + L  2 n–1 2 1 2 n–1 2 n

ML (H O) + L   ML + H O ; K = [ML ] / {[ML (H O)] [L]}

n–1 2 n 2 n n n–1 2

 ML n  nH 2 O
M(H 2 O) n  nL 
 n = K1 × K2 × K3 × ........ × Kn
  n, the stability constant, is related to thermodynamic stability when the system has reached equilibrium.
Most of the measurements have been made from aqueous solutions, which implies that the complex is
formed by the ligand displacing water from the aqua complex of the metal ion. Ignoring the charge and
taking L as an unidentate ligand, the stepwise formation of the complex is represented as shown above. K1,
K2, K3 ..... Kn representing the stepwise stability (or formation) constants.
 The above is thermodynamic stability criteria, there can be another kind of stability called kinetic stability,
which measures the rate of ligand replacement.

SOME IMPORTANT GENERALISATION REGARDING STABILITY CONSTANTS :

 For a given metal and ligand the stability is generally greater when the charge on the metal ion is greater.
Thus, stability of coordination entities of ions of charge 3+ is greater than the entities of 2+ ions. Further,
for the divalent ions of the first row transition elements, irrespective of the ligand involved, the stabilities
vary in the Irving-Williams order :
MnII < FeII < CoII < NiII < CuII > ZnII
 This order is according to the size of the ions, smaller the size of the ion or greater the charge density on the
metal greater is the stability of the complex.
In F¯, Cl¯, Br¯, I¯ ; F¯ forms strongest complexes due to small size & hence high charge density.
 The stability also depends on the formation of chelate rings. If L is an unidentate ligand and L – L, a
didentate ligand and if the donor atoms of L and L – L are the same element, then L – L will replace L. The
stabilisation due to chelation is called the chelate effect. It is of great importance in biological systems and
analytical chemistry.
 If a multidentate ligand happens to be cyclic and there are no unfavourable steric effects, a further increase
in stability occurs. This is termed the macrocyclic effect.

9.6 BONDING IN METAL CARBONYLS P.No.: 261

Compounds of metals with CO as a ligand are called metal carbonyls.

They are of two types.

MONOMERIC

 Those metal 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);
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Coordination Compounds 143

 [Cr(CO)6] (d2 sp3, octahedral) ; [V(CO)6] (d2 sp3, octahedral, only carbonyl which is paramagnetic having
one unpaired electron ; this is least stable among all the four carbonyls)
CO CO CO
OC CO CO

Ni Fe CO Cr

OC CO OC CO CO
CO CO CO
Ni(CO)4 Fe(CO)5 Cr(CO)6
Tetrahedral Trigonal bipyramidal Octahedral

POLYMERIC
 Those metal carbonyls which contain two or more than two metal atoms per molecule and they have
metal-metal bonds are called polymeric carbonyl. For examples : Mn2 (CO)10, Co2(CO)9, etc.

CO CO CO CO
CO CO OC CO
OC Mn Mn CO Co Co

CO CO OC OC CO
CO CO CO
[Mn2(CO)10] [Co2(CO)8]
 Metal carbonyls are mostly solids at room temperature and atmospheric pressure.
 The mononuclear 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 are more deeply coloured. Fe3(CO)12, dodecacarbonyltriiron(o), For examples : 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  and  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.

p p*

M s C  O


 p
Synergic bonding
1. 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.
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144 Coordination Compounds

2. 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–.

Sigma () bonded organometallic compounds :

 In these complexes, the metal atom and carbon atom of the ligand Bridging groups
are joined together with a sigma bond in which ligand contrib-
utes one electron and is therefore called one electron donor. CH3 CH3 CH3
For example ;
Al Al
1. Grignard’s Reagent : R – Mg – X where R is a alkyl or aryl
group and X is halogen. CH3 CH3 CH3
2. (CH3)4 Sn, (C2H5)4 Pb, Al2 (CH3)6, Al2 (C2H5)6 etc.

Pie ()-bonded organometallic compounds :

These are the compounds of metal with alkenes, alkynes, benzene and other ring compounds.

Zeise's salt :
 In Zeise’s salt structure, the ethylene occupies the fourth coordination site of the square planar complex
with the C — C axis perpendicular to the platinum ligand plane.
 Relative to free ethylene the C — C bond is lengthened (from 133.77 H H –
pm to 137.5 pm), and the hydrogen are slightly tilted back from a C
planar arrangement. ||
 The bond between the ethylene molecule and the metal ion may be Cl C
K+
considered as a dative  bond to an available orbital on the metal.
Pt H H
 The bonding scheme is analogous to that in carbon monoxide com-
plexes in which there is a ligand metal  donation and a reciprocal Cl Cl
metal to ligand  bonding. The extent of back bonding varies depend-
ing on the metal, the substituents on ethylene, and the other ligands K [PtCl3 (2 – C2H4)]
on the metal,

Ferrocene and bis(benzene) chromium :

 Ferrocene obeys 18-electrons rule. Depending on the electron counting method adopted, the cyclopentadienyl
ligand may be viewed as either a five electron donor (neutral atom) or a six electron donor (oxidation state).
 Similarly, the benzene ligand may be viewed as a six electron donor in neutral atom as well as in the
oxidation state. Ferrocene show thermal stability and is not oxidised by air.

–1

Fe 2+ Cr
Fe (5 – C5H5)2 and Cr (6 – C6H6)2
–1
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Coordination Compounds 145

9.8 P.No.: 261

 Coordination compounds are of great importance in biological systems. Example being – chlorophyll (the
green pigment in plants); haemoglobin (the red pigment of blood, which acts as oxygen carrier) along with
myoglobin (which stores oxygen and is a regulator of respiration); Vitamin B12, cyanocobalammine, the
anti-pernicions anaemia factor. All of these, respectively, are the coordination compounds of magnesium,
iron and cobalt with the macrocyclic porphyrin and corrin ligands.
 There are many examples of the use of coordination compounds in qualitative and quantitative chemical
analysis. The familiar colour reactions given by metal ions with a number of ligands (especially the chelat-
ing ligands), as a result of formation of coordination entities, form the basis for their detection and estima-
tion by classical and instrumental methods of analysis. Familiar examples of such reagents are :
ethylenediaminetetraaceticacid (EDTA), dimethylglyoxime, a-nitroso b-naphthol, cupron, etc.
 Some important extraction processes of metals, like those of extraction of silver and gold, make use of complex
formation. Gold, for example, combines with cyanide in the presence of oxygen and water to form the coordina-
tion entity [Au(CN)2]– in aqueous solution. Gold can be precipitated from this solution by the addition of Zinc.
 Purification of metals can be achieved through formation and subsequent decomposition of their coordination
compounds. For example, impure nickel is converted to [Ni(CO)4], which is decomposed to yield pure nickel.
 EDTA is used in the treatment of lead poisoning. Some coordination compounds of platinum effectively
inhibit the growth of tumors. Examples are : cis-platin (cis-[Pt(NH3)2Cl2] and related compounds.
 Organometallic compounds are used as catalysts. These catalysts are either of the homogeneous type (soluble
in the reaction medium) or of the heterogeneous type (insoluble in the reaction medium). The catalysed
polymerisation of alkenes at atmospheric pressure and ambient temperature using Ziegler-Natta catalyst
(titanium tetrachloride plus triethylaluminium) is one of the important discoveries of organometallic
chemistry. The first effective homogeneous catalyst chloridotris(triphenylphosphine) rhodium(I),
[RhCl(PPh3)3] for hydrogenation was given by Wilkinson.
 Tetra ethyl lead (TEL) is used as antiknock compound in gasoline.

08 111. Ammonia forms the complex [Cu(NH3)4] 2+ with copper

ions in alkaline solution but not in acid solution. The
106. Chlorophyll is a coordination compound having central reason for it is:
atom of (1) in alkaline solution Cu(OH)2 is precipitated which
(1) Ca (2) K is soluble in excess of alkali
(3) Na (4) M g (2) in acidic s olution protons coord inates with
107. A reagent used for identifying nickel ion is: ammonia molecule forming NH 4+ ions and NH 3
molecules are not available.
(1) potassium ferrocyanide
(2) dimethylglyoxime (3) copper hydroxide is amphoteric
(3) phenolphthalein (4) in acidic solution hydration protects Cu2+ ions
(4) EDTA 112. Which of the following compounds is brown coloured?
108. The bond length of C – O bond in carbon mono-xide is (1) Fe[Fe(CN)4] (2) Fe4[Fe(CN)6]
1.128 A. The C – O bond in Fe(CO)5 is: (3) Fe[Fe(CN)6] (4) K2Fe[Fe(CN)6]
(1) 1.128 Å (2) 1.72 Å 113. Which one of the following statement is correct?
(3) 1.118 Å (4) 1.15 Å (1) Ferric ions give a deep green precipitate on adding
109. Backbonding involves the formation of potassium ferrocyanide solution.
(1) -bond (2) coordinate bond (2) On boiling a solution having K+, Cu2+ & HCO3– ions,
(3) -bond (4) none of these we get a precipitate of K2Ca(CO3)2
110. Composition of complex formed when the ore argentite (3) Manganese s alt give a violet bo rax test in
is treated with NaCN is reducing flame
(1) Na[Ag(CN)2] (2) Na3[Ag(CN)6] (4) From a mixed precipitate of AgCl and AgI, ammonia
(3) Na[Au(CN)6] (4) Na[Au(CN)6] solution dissolves only AgCl
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146 Coordination Compounds

114. Coordination compounds have great importance in (4) CuSO4 + 4KCN  K2[Cu(CN)4] + K2SO4
biological systems. In this context which of the 118. Which of the following observations/statements is/
following statements is incorrect: are correct?
(1) Carboxypeptidase A is an enzyme and contains (1) Anhydrous CuSO 4 becomes blue in aqueous
zinc medium due to the complex formation
(2) Haemoglobin is the red pigment of blood and (2) Ni(CN) 2 dissolves in KCN giving an orange-red
contains iron solution
(3) Cyanocobalamin in B12 and contains cobalt (3) Fe(OH)3 can be precipitated by adding NH4OH to
(4) Chlorophylls are green pigments in plants and K3[Fe(CN)6]
contain calcium (4) None of the above
115. Aqua regia reacts with Pt to yield: 119. Which one of the following statements is incorrect?
(1) Pt(NO3) 4 (2) H2PtCl6 (1) Greater the stability constant of a complex ion,
(3) PtCl4 (4) PtCl2 greater is its stability
116. Which of the following is  complex? (2) Greater the charge on the central metal ion, greater
(1) Trimethyl aluminium (2) Ferrocene is the stability of the complex
(3) Diethyl zinc (4) Nickel carbonyl (3) Greater the basic character of the ligand, the
greater is the stability of the complex
117. The equation which is balanced and represents the
correct product(s) is (4) Complexes have low stability constants.
(1) Li2O + 2KCl  2LiCl + K2O 120. In Fe(CO)5, the Fe–C bond possesses:
(2) + + 2+
[CoCl(NH3)5] + 5H  CO + 5NH4 + Cl + – (1) –character only
Excess NaOH
(2) Both  and  characters
(3) [Mg(H2O)6] 2+ + (EDTA)4   (3) Ionic character
[Mg(EDTA)2+ + 6H2O (4) –character only

9.9 Synopsis
 When solutions of two or more simple stable compounds in molecular proportions are allowed to evapo-
rate, crystals of new compounds may be formed. These compounds compounds molecular or addition
compounds. Addition compounds are of two types :
1. Double salts or lattice compounds and 2. Coordination or complex compounds.
 The addition compounds which are stable in solid state but are broken down into individual constituents
when dissolved in water are called double salts. Mohr salt, potash alum, carnallite, etc., are some examples
of double salts.
 The addition compounds which retain their identity in solid state as well as in solunon are termed
coordination or complex compounds. In these compounds at least one complex ion is present. In complex
ion, a metal atomm or ion is surrounded by a number or groups through coordination.
 Complex compounds are mainly formed by transition metals but to a small extent by other metals such as
magnesium in chlorophyll. Transition metals form complexes due to the following reasons :
(i) small size, (ii) high nuclear charge, (ii) a number of vacant orbitals of equivalent energy where the
electrons donated by ligands are accommodated.
 The neutral molecules, anions or cations which are directly linked with the central metal atom or ion in a
complex ion are called ligands. The ligand at least consists one donor atom having a lone pair of electrons
which it can donate to metal atom or ion. Ligands can be classified on the basis of number of donor atoms.
They are termed monodentate, bidentate, tridentate, etc. The ligands having two or more donor groups are
called polydentate. Polydentate ligand is known as chelating ligand if on coordination it results in the
formation of a closed or cyclic ring structure. The complexes, thus, formed are called chelates.
 The number of atoms of the ligands that are directly bound to the central metal atom or ion by coordinate
bonds is known as coordination number of the metal atom or ion. It is actually the number of chemical
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Coordination Compounds 147

bonds which the ligands form with central metal atom or ion. The most common coordination numbers are
4 or 6. 1he central metal atom or ion and the ligands that are directly attached to it are enclosed in a square
bracket. This is called coordination sphere. It behaves as a single unit. The ions present outside the coor-
dination sphere form ionisation sphere.
 4K   [Fe(CN)6 ]4 
K 4 Fe(CN)6 

 [Cu(NH3 )4 ]2   SO 24 
[Cu(NH3 )4 ] SO 4 
Charge on the complex ion = oxidation number of metal ion + charge on the ligands

Coordination [Co(NH3) 6 ] Cl3 Ionisation

sphere sphere

Central metal Coordination

ion / atom Ligands Number
 Effective Atomic Number (EAN) is defined as the resultant number of electrons with the metal atom or ion
after gaining electrons from donor atoms after ligands.
EAN = atomic number of the metal – number of electrons lost in ion formation
+ number of electrons gained from the donor atoms of the ligands
 The ollowing points are follov in naming complex compounds :
1. Cation is named first followed by anion.
2. In the coordination sphere, the ligands are named lphabetically. Anionic ligands ending with -ide are
named by replacing -ide by suffix -o or by replacing -e by -o. Ligands whose names end in -ite or -ate
become -ito or -ato, i.e., by replacing the ending -e with -o. Neutral ligands are given the same names
as the neutral molecules. However, H2O is named aqua and NH3 ammine. Positively charged ligands
have suffix -ium. If the number of a particular ligand is more than one, the number is indicated by
using di, tri, tetra, penta, etc. However, when the name of the ligand includes number, then bis, tris,
etc., are used.
3. The oxidation state of the central metal is shown by Roman numeral in bracket immediately following
its name.
4. Complex positive ions and neutral coordination compounds have no special ending but complex
negative ions always end in the suffix -ate.
 Coordination compounds exhibit structural isomerism ds well as stereoisomerism. Structural 1somerism is
displayed when different ligands are present within Oordination spheres. The coordination compounds
exhibit various types of structural isomerism.
1. Ionisation isomerism : Isomers give different ions in solution.
Examples : [Co(NH3)5Br] Cl ; [Co(NH3)5Cl]Br.
2. Hydrate isomerism : Isomers having H2O as a ligand or as water of hydration.
Examples : [Cr(H2O)6]Cl3 ; [CrCl(H2O)5] Cl2 . H2O ; [CrCl2(H2O)4] Cl . 2H2O.
3. Coordination isomerism : The ligands interchanged in both the cationic and anionic ions.
Examples : [Co(NH3)6] [Cr(CN)6] ; [Cr(NH3)6] [Co(CN)6]
4. Linkage isomerism : This type of isomerism exists when ambidentate ligand is present.
Examples : [Co(NH3)5ONO]Cl2 ; [Co(NH3)5 NO2] Cl2.
 Stereoisomerism : It arises on account of the different positions and arrangement of ligands in space
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148 Coordination Compounds

around the metal ion. It is of two types : (a) geometrical and (b) optical
Geometrical isomerism is common in coordination number 4 (square planar) and coordination number 6
compounds. This type of isomerism is termed cis-trans isomerism. When the ligands occupy adjacent
positions, the isomer is called cis-form and when opposite positions, the isomer is termed trans-isomer.
The square planar complexes having general formula Ma2b2 Ma2bc or Mabcd show cis-trans isomerism.
Square planar complexes having unsymmetrical bidentate ligands can also show geometrical isomerism.
Geometrical isomerism is not observed in complexes o coordination numbers 2 and 3. Square planar
complexes of the type Ma4, Ma3b and Mab3 do not show geometrical isomerism. Geometrical isomerism is
also not observed in tetrahedral complexes. Octahedral complexes of the type Ma4b2, Ma2b4 Ma4bc and
Ma3b3 exhibit geometrical isomerism.
 A coordination compound which can rotate the plane of polarised light is said to be optically active. The
optical isomers are pair of molecules which are non-superimposable mirror images of each other. The
isomer which rotates the plane of polarised light to right direction is termed dextro while the isomer which
rotates the plane of polarised light to left direction is termed laevo form.
Optical isomerism is very common in octahedral complexes. Octahedral compounds of general formulae
[Ma 2 b 2 c 2 ] n± [Mabcdef], [M(AA) 3] n±, [M(AA) 2 a 2 ] n± , and [M(AB) 3] n± and [M(AA) 2ab] n± where AA =
symmetrical bidentate ligands and AB = unsymmetrical bidentate ligands.
 Werner, in 1893, proposed the coordination theory to explain the properties and structures of various metal
ammines. The important postulates of the theory are :
1. Every valencies exhibits two types of valencies :
(a) Primary valency and (b) Secondary corresponds to oxidation state of metal and secondary valency
represents the coordination number of the metal. Primary valency is satisfied by negative ions and is
ionisable. The secondary valency is satisfied by neutral molecules or negative 1ons or both. This
valency is non-ionic. Metal and neutral molecules or negative ions which satisfy secondary valency
are enclosed in square bracket and termed as coordination sphere.
2. Every element tends to satisfy both its valencies. A negative ion when present in coordination sphere
shows a dual behaviour. It satisfies both primary and secondary valencies. The presence of negative
ion in the coordination sphere reduces the charge on the complex ion by the amount of charge
possessed by it and the negative ions present in the coordination sphere are not ionised.
3. The ligands in coordination sphere are directed towards fixed positions in space. The geometry of the
complex ion depends on coordination number. If the coordination number is 6, the complex is octahe-
dral. On the other hand, if the coordination number is 4, the geometry of the complex may be tetrahe-
dral or square planar.
 Valence bond theory describes the bonding in complexes in terms of two-electron, coordinate-covalent
bonds resulting from overlap of filled ligand orbitals with vacant metal hybrid orbitals that point in the
direction of the ligands :
sp (inear) ; sp3 (tetrahedral); dsp2 (square planar) and d2sp3 and sp3d2 (octahedral).
This theory explains with reasonable success the formation, magnetic behaviour and geometrical shapes of
coordination compounds. It, however, fails to provide a quantitative interpretation of magnetic behaviour
and explanation about optical properties of coordination compounds.
Examples:
(a) Octahedral complexes
1. Inner orbital (low spin) complexes involving d sp-hybridization:
[Fe(CN)6]3–, [Co(CN)6]3–, [Cr(NH3)6]3+. [Co(NH3)6]3+, etc.
2. Outer orbital (high spin) complexes involving sp3d2-hybridization :
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Coordination Compounds 149

[CoF]3–, [Fe(H2O)6]3+. [MnF6]3–, [Ni(NH3)6]2+, etc.
(b) Tetrahedral complexes involving sp3-hybridization :
[NiCl4]2–, [Cu(Cl4)]2–, Ni(CO)4, [Zn(NH3)4]2+, etc.
(c) Square planar complexes involving dsp2-hybridization :
[Ni(CN)4]2–, [Cu(NH3)4]2+, etc.
 Crystal field theory assumes that the metal-ligand bonding is entirely ionic. Because of electrostatic
repulsions between the d-electrons and the ligands, the d-orbitals are raised in energy and are diferentiated
by an energy separation called the crystal field splitting, . In octahedral complexes the d z , d x
2 2
 y2 orbitals
(e.g. set of orbitals) have higher energy than d xy, dyz and dzx orbitals (eg., set of orbitals). Tetrahedral
complexes exhibit just opposite splitting pattern.
The colours of complexes are due to electronic transitions from one set of d-orbitals to another and the
transition energies depend on the position of ligand in the spectrochemical series. Weak field ligands give
small  values and strong field ligands give small  values. Crystal field theory accounts for magnetic
properties of complexes in terms of the relative values  and the spin pairing energy. Small  values favour
hi spin complexes (maximum number of unpaired d-electrons) and large  values favour low complexes.
 In general, higher the charge density on the central ion, the greater is the stability of its complexes.
Electronegativity of the central 1on aiso intluences the stability. The higher the oxidation state of the metal,
the more stable is the complex. The more basic ligand forms the complex with greater stability.
The cyano and ammine complexes are far more stable than those formed by halide ions.
Chelating ligands form more stable complexes as compared to monodentate ligands.
 Coordination compounds are generally prepared by the application of :
1. Ligand substitution reactions :
[Cu(H 2 O)4 ]2  4NH3 
[Cu(NH3 )4 ]2  4H 2 O
2. Direct mixing of reagent :
PtCl2  2H 2 N — CH 2 — CH 2 — NH2 
[Pt(en)2 Cl2 ]
3. RedOX reaction :
K 2 Cr2 O7  7H 2 C2 O4  2K 2 C2 O4 
 2K 3 [Cr(C2 O4 )3 ]  6CO2  7H 2 O
 The complexes find applications in various fields :
1. Analytical chemistry : Cu2+, Fe3+, Ni2+, etC. tested in the form of complexes. Ca2+, Mg2+ and Zn2+ ions
are estimated volumetrically by EDTA. Mauy ions are quantitatively estimated by using a numo of
organic ligands.
2. Coordination complexes of transition metals exhibit a variety of colours. This forms the basis of colo-
rimetric estimations.
3. Complexes act as oxidation reduction indicators and sequestering reagents. Hardness of water is
estimated by use of EDTA.
4. Silver and gold are extracted by the use of complex formation.
5. Fixing of negative is done in photography by use of hypo solution. It forms soluble complex with
silver bromide.
6. During electroplating, complexes are used in electrolytue bath.
7. Cis-platin, [Pt(NH3)2Cl2], is used in the treatment of cancer.
British anti-lewisite (BAL) is used as antidote for treating poisoning by As, Hg, Au, Bi, Pb and Cd.
8. Haemoglobin is a complex of Fe, chlorophyll is complex of Mg, vitamin B12 is a complex of cobalt.
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150 Coordination Compounds

1. An aqueous solution of CoCl 2 on addition of excess 10. Assertion : [Co(NO 2 ) 3(NH 3 ) 3] does not show optical
of concentrated HCl turns blue due to formation of : isomerism.
(1) [Co(H2O)4Cl2] (2) [Co(H2O)2Cl4] 2– Reason : It has a plane of symmetry.
2–
(3) [CoCl4] (4) [Co(H2O)2Cl2] (1) If both Assertion and Reason are true and the
2. In whi ch of th e fo llo wi ng pairs, bo th th e co m- reason is the correct explanation of Assertion.
plexes show optical isomerism ? (2) If both Assertion and Reason are true but rea-
(1) cis-[Cr(C2O4)2Cl2]3–, cis-[Co(NH3)4Cl2] son is not the correct explanation of Assertion.
(2) [Co(en)3] Cl3, cis-[Co(en)2Cl2]Cl (3) If Assertion is true but Reason is false.
(3) [PtCl(dien)Cl] , [NiCl2Br2]2– (4) If both Assertion and Reason are false.
(4) [Co(NO3)3(NH3)3], cis-[Pt(en)2Cl2] 11. [Fe(NO2)3Cl3] and [Fe(O – NO)3Cl] shows :
3. The diamagnetic species is : (1) Linkage isomerism
(1) [Ni(CN)4]2– (2) [NiCl4]2– (2) Geometrical isomerism
2–
(3) [CoCl4] (4) [CoF6] 2– (3) Optical isomerism
4. The correct order for the wavelength of absorption in (4) None of the above
the visible region is : 12. Which of the following coordination entities should
(1) [Ni(NO2)6] 4– < [Ni(NH3)6] 2+ < [Ni(H2O)6] 2+ be expected to absorb light of lowest frequency?
(2) [Ni(NO2)6]4– < [Ni(H2O)6] 2+ < [Ni(NH3)6] 2+
(3) [Ni(H2O)6]2+ < [Ni(NH3)6]2+ < [Ni(NO2)6] 4+ (1) [Cr(en)3]3+ (2) [CrCl6]3–
3+
(4) [Ni(NH3)6] 2+ < [Ni(H2O)6] 2+ < [Ni(NO2)6] 4– (3) [Cr(NH3)6] (4) [Cr(CN)6]3–
5. Assertion : Potassium ferrocyanide is diamagnetic, 13. Assertion : When NO reacts with FeSO 4 , a brown
whereas potassium ferricyanide is paramagnetic. coloured complex is formed.
Reason : Crystal field splitting in ferrocyanide ion is Reason : In the complex, the coordination number
greater than that of ferricyanide ion. of Fe is 6.
(1) If both Assertion and Reason are true and the (1) Both A and R are true and R is the correct expla-
reason is the correct explanation of Assertion. nation of A.
(2) If both Assertion and Reason are true but rea- (2) Both A and R are true but R is not correct explana-
son is not the correct explanation of Assertion. tion of A
(3) If Assertion is true but Reason is false. (3) A is true but R is false
(4) If both Assertion and Reason are false. (4) A is false but R is true
6. Among the following, the species having square pla- (5) Both A and R are false
nar geometry for central atom are : 14. For the square planar complex [M(a) (b) (c) (d)] (where,
I. [XeF4] II. SF 4 M =central metal ; a, b, c and d are monodentate
III. [NiCl4] 2–
IV. [PtCl4] 2– ligands) the number of possible geometrical isomers
(1) I and IV (2) I and II are
(3) II and III (4) III and IV (1) 1 (2) 2
7. The pair in which both species have the same mag- (3) 3 (4) 4
netic moment (spin only) value is : 15. Assertion : CO and CN are referred as  acid ligands.
(1) [Cr(H2O)6]2+, [CoCl4]2– Reason : In CO and CN vacant  type orbitals are
(2) [Cr(H2O)6]2+, [Fe(H2O)6] 2+ present.
(3) [Mn(H2O)6] 2+, [Cr(H2O)6] 2+ (1) Both A and R are true and R is the correct expla-
(4) [CoCl4]2–, [Fe(H2O)6] 2+ nation of A.
8. The number of possible isomers of an octahedral com- (2) Both A and R are true but R is not correct explana-
plex [Co(C2O4)2(NH3)2] – is : tion of A
(1) 1 (2) 2 (3) A is true but R is false
(3) 3 (4) 4 (4) A is false but R is true
9. The ligands in anti-cancer drug cis-platin are : 16. Which one has the highest paramagnetism ?
(1) NH3,Cl (2) NH3H2O (1) Ni(CO)4 (2) [Co(NH3)6]Cl3
(3) Cl, H2O (4) NO, Cl (3) [Ni(NH3)6]Cl2 (4) [Cu(NH3)4]Cl2
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Coordination Compounds 151

17. Assertion : K4[Fe(CN)6] is diamagnetic and [Fe(H2O)6] (1) d4 (in strong field ligand)
Cl3 is paramagnetic. (2) d4 (in weak field ligand)
Reason : Hybridisation of central metal in [Fe(H2O)6]Cl3 (3) d3 (in weak as well as strong field ligand)
is sp3d2, while in K4[Fe(CN)6] is d2sp3. (4) d5 (in strong field ligand)
(1) Both A and R are true and R is the correct 29. Which one of the following complexes would exhibit the
explanation of A. lowest value of paramagnetic behaviour ?
(2) Both A and R are true but R is not correct
(1) [Co(CN)6]3– (2) [Fe(CN)6] 3–
explanation of A
(3) [Mn(CN)6] 3– (4) [Cr(CN)6]3–
(3) A is true but R is false
30. Nickel (Z = 28) combines with a uninegative
(4) A is false but R is true
monodentate ligand X– to form a paramagnetic complex
18. Which of the following is potassium ferricyanide? [NiX4] 2– The number of unpaired electron(s) in the nickel
(1) [K4[Fe(CN)6] (2) K3[Fe(CN)6] and geometry of this complex ion are, respectively :
(3) K3[Fe (CN)3] (4) K3[Fe(CN)4] (1) one, tetrahedral (2) two, tetrahedral
19. Which does not give a precipitate with AgNO 3 (3) one, square planar (4) two, square planar
solution?
31. The IUPAC name for the complex [Co(NO2) (NH3)5]Cl2
(1) [Co(NH3)6Cl3 (2) [Co(NH3)5Cl]Cl2 is :
(3) [Co(NH3)4Cl2]Cl (4) [Co(NH3)3Cl3] (1) Nitrito-N-pentaamminecobalt(III) chloride
20. In the complex ion [Co(NH 3 ) 6 ] 3+ , the NH 3 molecules
(2) Nitrito-N-pentaamminecobalt(II) chloride
are linked to the central metal ion by
(3) Pentaamminenitrito-N-cobalt(II) chloride
(1) ionic bonds (2) covalent bonds
(4) Pentaamminenitrito-N-cobalt(III) chloride
(3) coordinate bonds (4) hydrogen bonds
32. In Fe(CO)5, the Fe – C bond possesses :
21. A magnetic moment of 1.73 BM will be shown by one
among the following : (1) -character only
(1) [Ni(CN)4]2– (2) TiCl4 (2) both  and  characters
(3) [CoCl6]4– (4) [Cu(NH3)4]2+ (3) ionic character only
22. An excess of AgNO3 is added to 100 mL of a 0.01M (4) -character only
solution of dichlorotetraaquachromium (III) chloride. 33. How many EDTA (ethylenediaminetetraacetic acid)
The number of moles of AgCl precipitated would be : molecules are required to make an octahedral complex
(1) 0.002(2) 0.003 with a Ca2+ ion ?
(3) 0.01 (4) 0.001 (1) Six (2) Three
23. Among the following complexes the one which shows Zero (3) One (4) Two
crystal field stabilizations energy (CFSE) 34. The ‘spin only’ magnetic moment (in units of Bohr
(1) [Nn(H2O)6] 3+ (2) [Fe(H2O)6] 3+ magneton, µ B) of Ni 2+ in aqueous solution would be
(3) [Co(H2O)6] 2+
(4) [Co(H2O)6] 3+ (atomic number Ni = 28)
24. Which of the following complexes is used to be as an (1) 2.84 (2) 4.80
anticancer agent ? (3) 0 (4) 1.73
(1) mer – [Co(NH3)3Cl] (2) cis – [PtCl2(NH3)2] 35. Which one of the following has a square planar
(3) cis – K2[PtCl2Br2] (4) Na 2CoCu geometry?
25. The oxidation state of Cr in [Cr(NH3)4Cl2] + is : (1) [NiCl4]2– (2) [PtCl4] 2–
2–
(1) 0 (2) +1 (3) [CoCl4] (4) [FeCl4] 2–
(3) +2 (4) +3 (At. no. Co = 27, Ni = 28, Fe = 26, Pt = 78)
26. The IUPAC name of K3Fe(CN)6 is : 36. The coordination number and the oxidation state of
(1) Potassium hexacyanoferrate(II) the element 'E' in the complex [E(en)2(C2O4)] NO2 (when
(2) Potassium hexacyanoferrate(III) 'en' is ethylene diamine) are, respectively,
(3) Potassium hexacyanoiron(II) (1) 4 and 2 (2) 4 and 3
(4) Tripotassium hexacyanoiron(II) (3) 6 and 3 (4) 6 and 2
27. Which of the following will show optical isomerism 37. In which of the following octahedral complexes of Co (at
? no. 27), will the magnitude of 0 be the highest?
(1) [Cu(NH3)4]2+ (2) [ZnCl4] 2– (1) [Co(C2O4)3] 3– (2) [Co(H2O)6] 3+
3+
(3) [Cr(C2O4)3]3– (4) [Co(CN)6]3– (3) [Co(NH3)6] (4) [Co(CN)6]3–
28. The value of ‘spin only’ magnetic moment for one of 38. Which of the following has an optical isomer ?
the following configurations is 2.84 BM. The correct (1) [Co (en) (NH3)2] 2+ (2) [Co(H2O)4 (en)] 3+
one is : (3) [Co (en)2 (NH3)2] 3+
(4) [Co (NH3)3 Cl]+
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152 Coordination Compounds

39. Which of the following pairs represents linkage iso- (1) [Co(en)3] 3+
mers ? (2) [Co(en)2 Cl2]+
(1) [Pd(PPh 3)2 (NCS)2] and [Pd(PPh 3)2 (SCN)2] (3) [Co(NH3)3 Cl3]
(2) [Co(NH3)5 NO3] SO4 and [Co (NH3)5 (SO4)] NO3 (4) [Co(en) (NH3)2 Cl2] +
(4) [PtCl2 (NH3)4 Br2 and [Pt Br2 (NH3)4] Cl2 46. The octahedral complex of a metal ion M3+ with four
(4) [Cu (NH3)4] [Pt Cl4] and [Pt (NH3)4 [CuCl4] monodentate ligands L1, L2, L3 and L 4 absorb wave-
40. A solution containing 2.675 g of CoCl3 . 6NH3 (molar lengths in the region of red, green, yellow and blue,
mass = 267.5 g mol–1) is passed through a cation ex- respectively. The increasing order of ligand strength
changer. The chloride ions obtained in solution were of the four ligands is :
treated with excess of AgNO3 to give 4.78 g of AgCl (1) L4 < L3 < L2 < L1 (2) L1 < L3 < L2 < L4
(molar mass = 143.5 g mol–1). The formula of the com- (3) L3 < L2 < L4 < L1 (4) L1 < L2 < L4 < L3
plex is (At. mass of Ag = 108 u) 47. Potassium ferrocyanide is a
(1) [Co(NH3)6] Cl3 (2) [CoCl2 (NH3)4] Cl (1) Normal salt (2) Mixed salt
(3) [CoCl3(NH3)3] (4) [CoCl(NH3)5] Cl2 (3) Double salt (4) Complex salt
41. Which one of the following has an optical isomer ? 48. The chemical formula of diammine silver (I) chloride is
(1) [Zn(en)(NH3)2] 2+ (2) [Co(en)3] 3+ (1) [Ag(NH3)]Cl (2) [Ag(NH3)2]Cl
3+
(3) [Co(H2O) 4(en)] (4) [Zn(en)2] 2+ (3) [Ag(NH3)2]Cl (4) [Ag(NH4)2]Cl
(en = ethylenediamine) 49. A square planar complex represented as:
42. Which among the following will be named as NH2 NH2
dibromidobis (ethylene diamine) chromium (III) bro- CH2 CH2
mide?
(1) [Cr(en)3]Br3 (2) [Cr(en)2Br2]Br CH2 CH2
(3) [Cr(en)Br4]– (4) [Cr(en)Br2]Br H2N H2N
43. The magnetic moment (spin only) of [NiCl4] 2– is : (1) Geometrical isomerism
(1) 1.82 BM (2) 5.46 BM (2) Linkage isomerism
(3) 2.82 BM (4) 1.41 BM (3) Optical isomerism
44. Which of the following facts about the complex (4) None of these
[Cr(NH3)6]Cl3 is wrong ? 50. Which of the following facts about the complex
(1) The complex involves d 2sp 3 hybridisation and is [Cr(NH3)6]Cl3 is wrong:
octahedral in shape. (1) The complex involves d 2sp 3 hybridization and is
(2) The complex is paramagnetic. octahedral in shape
(3) The complex is an outer orbital complex. (2) The complex is paramagnetic
(4) The complex gives white precipitate with silver (3) The complex is an outer orbital complex
nitrate solution. (4) The complex gives white precipitate with silver
45. Which of the following complex species is not expected nitrate solution.
to exhibit optical isomerism ?
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Coordination Compounds 153

(Concept Builder)

1. Which of the following complex formed by Cu2+ ions is (1) [Cr(H2O)4Cl2]+ (2) [Pt(NH3)3 Cl]
most stable? (3) [Co(NH3)6] 3+
(4) [Co(CN)5(NC)]3–
 [Cu(NH3)4]2+, log K = 11.6
(1) Cu 2+ + 4NH3 
8. The CFSE for octahedral [COCl6] 4– is 18,000 cm–1. The
(2)  [Cu(CN)4]2–, log K = 27.3
Cu 2+ + 4CN–  CFSE for tetrahedral [COCl4] 2– will be
(3)  [Cu(en)2]2+, log K = 15.4
Cu 2+ + 2en  (1) 18,000 cm–1 (2) 16,000 cm–1
(4)  [Cu(H2O)4]2+, log K = 8.9
Cu 2+ + 4H2O  (3) 8,000 cm –1
(4) 20,000 cm–1
2. The colour of the coordination compounds depends 9. Due to the presence of ambident ate ligands
on the crystal field splitting. What will be the correct coordination compounds show isomerism. Palladium
order of absorption of wavelength of of light in the complexes of t he type [Pd(C 6 H 5 ) 2 (SCN)] 2 and
visible region, for the complexes, [Co(NH 3 ) 6 ] 3+ , [Pd(C6H5)2(NCS)2] are
[Co(CN)6] 3– , [Co(H2O)6] 3+? (1) linkage isomers
(1) 3– 3+
[Co(CN)6] > [Co(NH3)6] > [Co(H2O)6] 3+ (2) coordination isomers
(2) [Co(NH3)6] 3+ > [Co(H2O)6] 3+ > [Co(CN)6] 3– (3) ionization isomers
(3) [Co(H2O)6] 3+ > [Co(NH3)6] 3+ > [Co(CN)6] 3– (4) geometrical isomers.
10. The compoun ds [Co(SO 4 )(NH 3 ) 5 ]Br and
(4) [Co(NH3)6] 3+ > [Co(CN)6] 3– > [Co(H2O)6] 3+
[Co(SO4)(NH3)5]Cl represent
3. When 0.1 mol CoCl 3(NH 3) 5 is treated with excess of
(1) linkage isomerism
AgNO3, 0.2 mol of AgCl are obtained. The conductivity
(2) ionization isomerism
of solution will correspond to :
(3) coordination isomerism
(1) 1:3 electrolyte (2) 1:2 electrolyte
(4) no isomerism.
(3) 1:1 electrolyte (4) 3:1 electrolyte
11. A chelating agent has two or more than two donor
4. When 1 mol CrCl3.6H2O is treated with excess of AgNO3, atoms to bind to a single metal ion. Which of the
3 mol of AgCl are obtained. The formula of the complex following is not a chelating agent?
is : (1) Thiosulphate (2) Oxalato
(1) [CrCl3 (H2O)3]·3H2O (3) Glycinato (4) Ethane-1, 2-diamine
(2) [CrCl2(H2O)4]Cl·2H2O 12. Which of the following species is not expected to be a
(3) [CrCl(H2O)5]Cl2·H2O ligand?
(4) [Cr(H2O)6]Cl3 (1) NO (2) NH4+
(3) NH2CH2CH2NH 2 (4) CO
5. The correct IUPAC name of [Pt(NH3)2Cl2] is
13. What kind of isomerism exists between [Cr(H2O)6]Cl3
(1) diamminedichloridoplatinum (II)
(violet) and [Cr(H2O)5Cl)Cl2.H2O (greyish-green)?
(2) diamminedichloridoplatinum (IV)
(1) Linkage isomerism
(3) diamminedichloridoplatinum (I)
(2) Solvate isomerism
(4) dichloridodiammineplatinum (IV)
(3) Ionisation isomerism
6. The stabilization of coordination compounds due to
(4) Coordination isomerism
chelation is called the chelate effect. Which of the
14. IUPAC name of [Pt(NH3)2Cl(NO2)] is
following is the most stable complex species?
(1) platinum diaminechloronitrite
(1) [Fe(CO)5] (2) [Fe(CN)6] 3–
(2) chloronitrito-N-ammineplatinum (II)
(3) [Fe(C2O4)3] 3– (4) [Fe(H2O)6] 3+
(3) diamminechloridonitrito-N-platinum (II)
7. Indicate the complex ion which shows geometrical
(4) diamminechloronitrito-N-platinate (II).
isomerism.
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154 Coordination Compounds

• Instructions for Questions 1 to 10 8. Assertion : Potassium ferrocyanide is diamagnetic

Given below are two statements: One is labelled as Assertion where as potassium ferricyanide is paramagnetic.
(A) and the other is labelled as Reason (R).
Reason : Crystal field splitting in ferrocyanide ion is
In the light of the above statements, choose the most greater than that of ferricyanide ion.
appropriate answer from the options given below :
9. Assertion : K 2 [PtCl 6 ] gives white ppt when reacts
(1) Both (A) and (R) are correct and (R) is the correct
with AgNO3.
explanation of (A)
(2) Both (A) and (R) are correct but (R) is not the correct Reason : Chloride ion in the complex is non-ionisable.
explanation of (A)
10. A s s e r t i o n : T r a n s [ C o C l 2( e n ) 2] + i s o p t i c a l l y
(3) (A) is correct the (R) is not correct inactive.
(4) (A) is not correct but (R) is correct
Reason : It has plane of symmetry.

1. Assertion : In the complex [Co(NH3)3 Cl3], chloride ions

satisfy the primary valencies as well as the secondary • Instructions for Questions 11 to 15
valencies of cobalt metal. Given below are two statements :
In the light of the above statements, choose the most appropriate
Reason : [Co(NH3)3Cl3] shows geometrical as well as
answer from the options given below :
optical isomerism.
(1) Both Statement I and Statement II are correct
2. Assertion : The complex [Cr(SCN)(NH3)5]Cl2 is linkage (2) Both Statement I and Statement II are incorrect
isomeric with [Cr(NCS)(NH3)5]Cl2.
(3) Statement I is correct but Statement II is incorrect
–
Reason : SCN is an ambident ligand in which there are (4) Statement I is incorrect but Statement II is correct
two possible coordination sites.
11. Statement I : The complex [Cr(SCN)(NH 3 ) 5]Cl 2 is
3. Assertion : [Co(NO 2) 3(NH 3) 3] does not show optical
linkage isomer with [Cr(NCS)(NH3)5]Cl2.
isomerism.
Statement II : SCN is an ambident ligand in which there
Reason : It has plane of symmetry.
are two coordination sites.
4. Assertion : In the co-ordination complex [Pt(NH3)4Cl2]
Br2, a yellow precipitate of AgBr is obtained on treat- 12. Statement I : The IUPAC name of K3[Cr(CN)6] is potas-
ing it with AgNO3 (aq). sium hexacyano chromate (III).

Reason : Bromide ions are present as counter ions in Statement II : It is an anion complex.
the ionization sphere.
13. Statement I : Charge on the complex of ferric ion with
5. Assertion : Co-ordination number of cobalt in the com- EDTA is minus one.
plex [Co(en)3] 3+ is six.
Statement II : EDTA is a hexadentate ligand.
Reason : Ethylenediamine acts as a bidentate ligand.
14. Statement I : Ti(H 2 O) 3+ is coloured ion while
6. Assertion : Charge on the complex of ferric ion with Sc(H 2 O)3+
6
is colourless.
EDTA is minus one.
Statement II : Ti3+ has 3d1 configuration whereas Sc3+
Reason : EDTA is a hexadentate ligand. has no unpaired electron and thus d-d transition is not
7. Assertion : The [Ni(en)3] Cl2 has higher stability than possible.
[Ni(NH3)6] Cl2. 15. Statement I : [Fe(H2O)5NO]SO4 is paramagnetic.
Reason : In [Ni(en)3] Cl 2, the geometry around Ni is Statement II : The Fe in [Fe(H 2O) 5NO]SO4 has three
octahedral.
unpaired electrons.
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Coordination Compounds 155

(Direct from
NCERT)

Match the List – I and List – II and choose the correct (2) (a) – (iv); (b) – (iii); (c) – (ii); (d) – (i)
combination from the options given. (3) (a) – (iii); (b) – (i); (c) – (vi); (d) – (ii)
(4) (a) – (i); (b) – (ii); (c) – (iii); (d) – (iv)
1. Match List – I with List – II
List – I List – II 4. Match List – I with List – II
(a) [Co(NCS)(NH3)5](SO3) (i) –1 List – I List – II
(b) Na[Co(CO)4] (ii) 0 (a) [Ma 3b 2c] (i) All stereoisomers are
(c) Na4[Co(S2O3)3] (iii) +1 optically inactive
(d) Co 2(CO)8 (iv) +2 (b) [Ma 3b 3] (ii) No. of geometrical
(v) +3 isomers = 2
Choose the correct answer from the options given below : (c) [Ma 3 bcd] (iii) No. of geometrical
isomer = 4
(1) (a) – (v); (b) – (i); (c) – (iv); (d) – (ii)
(d) [Ma 4 bc] (iv) Total 3 stereoisomers
(2) (a) – (iii); (b) – (i); (c) – (v); (d) – (ii)
(v) Only one enantiomeric
(3) (a) – (i); (b) – (iii); (c) – (vi); (d) – (i)
pair is possible
(4) (a) – (i); (b) – (iv); (c) – (v); (d) – (ii)
Choose the correct answer from the options given below :
2. Match List – I with List – II (1) (a) – (iii, i); (b) – (i, ii); (c) – (i, v); (d) – (i, ii)
List – I List – II (2) (a) – (i, iv); (b) – (i, ii); (c) – (iii, v); (d) – (i, ii)
(a) Ni(CO)4 (i) sp3 (3) (a) – (i, ii); (b) – (v, i); (c) – (i, ii); (d) – (i, iv)
(b) [Ni(CN)4]2– (ii) ds p 2 (4) (a) – (i, iv); (b) – (i, ii); (c) – (i, iv); (d) – (i, ii)
(c) [Fe(CN)6] 4– (iii) sp 3 d 2 5. Match List – I with List – II
(d) [MnF6] 3– (iv) d 2 sp 3
List – I List – II
(v) s p 2d
(a) Zeigler–Natta (i) Organomettali system
Choose the correct answer from the options given below :
catalyst
(1) (a) – (i); (b) – (iv); (c) – (v); (d) – (ii)
(b) Wilkinson (ii) Chelating ligard
(2) (a) – (v); (b) – (i, iii); (c) – (iv); (d) – (ii)
catalyst present
(3) (a) – (i); (b) – (ii); (c) – (vi); (d) – (iii)
(c) Ethylenediaminetetra (iii) dsp 2 -hybridisation
(4) (a) – (iii); (b) – (i); (c) – (v); (d) – (ii) acetatocalcate (II) ion
3. Match List – I with List – II (d) cis-platin (iv) can show optical or
geometrical isomerism
List – I List – II
(v) Having application
2-
(a) [Ni(CN)4] (i) tetrahedral in analytical
(b) [ZnCl4] 2- (ii) Tetragonal medicinal field
(c) [Co(en)3] 3+ (iii) Square planar Choose the correct answer from the options given below :
(d) [Cu(Cl4)]2- (iv) Square pyramid (1) (a) – (v); (b) – (i); (c) – (iv); (d) – (ii)
(v) Octahedral (2) (a) – (i); (b) – (iii); (c) – (ii); (d) – (v)
Choose the correct answer from the options given below : (3) (a) – (i); (b) – (iii); (c) – (vi); (d) – (i)
(1) (a) – (iii); (b) – (i); (c) – (v); (d) – (i) (4) (a) – (i); (b) – (iv); (c) – (v); (d) – (ii)
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156 Coordination Compounds

(Previous Year Questions)

1. Which one of the folloiwng octahedral complexes will 7. Which of the following does not have a metal-carbon
not show geemetrical isomerism? (A and B are bond ? [AIPMT-2004]
monodentate ligands) [AIPMT-2003] (1) Al(OC2H5) 3 (2) C2H5MgBr
(1) [MA4B2] (2) [MA5B] (3) K[Pt(C2H4)Cl3] (4) Ni (CO)4
(3) [MA2B4] (4) [MA3B3] 8. CN– is strong field ligand. This is due to the fact that
2. According to IUPAC nomenclature sodium nitroprusside (1) it carries negative charge [AIPMT-2004]
is named as [AIPMT-2003]
(2) it is a pseudohalide
(1) sodium pentacyanonitrosyl ferrate (II)
(3) it can accept electrons form metal species
(2) sodium pentacyanonitrosyl ferrate (III)
(4) if forms high spin complexes with metal species
(3) sodium nitoferricyanide
9. Considering H2O as weak field ligand, the number of
(4) sodium nitroferrocyanide
unpaired electrons in [Mn(H2O)6] 2+ will be (At. no. of
3. The number of unpaired electrons in the complex ion Mn = 25) [AIPMT-2004]
[COF6] 3– is (At.no.of Co =27) [AIPMT-2003]
(1) 3 (2) 5
(1) 3 (2) 2
(3) 2 (4) 4
(3) 2 (4) 0
10. Among [Ni(CO) 4], [Ni(CN) 4] 2-, [NiCl 4] -2 species, the
4. Among the following which is not the bonded
hybridisation states of the Ni atom are, arespectively
organometallic compound ? [AIPMT-2003]
(At no.of Ni = 28) [AIPMT-2004]
(1) K[PtCl3 (- C2H4)] (2) Fe ( -C5H5)2
(1) sp3, dsp2. dsp2 (2) sp3, dsp2. sp2
(3) Cr (-C6H6)2 (4) (CH3)4 Sn
(3) sp3, sp3. dsp2 (4) dsp2, sp3. sp3
5. Which of the following coordination compounds would
11. Which one of the following is an inner orbital complex
exhibit optical isomerism ? [AIPMT-2003]
as well as diamagnetic in behaviour? (At.No. Of Zn =
(1) Pentaamminenitrocobalt (III) iodide
30, Cr =24, Co =27, Ni=28) [AIPMT-2005]
(2) Diamminedichloroplatinum (II)
(1) [Zn (NH3)6] 2+ (2) [Cr (NH3)6] 3+
(3) Trans-Dicyanobis (ethylenediamine)
(3) [Co (NH3)6] 3+ (4) [Ni (NH3)6] 2+
chromium (III) chloride
12. Which one of the following is expected to exhibit optical
(4) Tris- (ethylenediamine) cobalt (III) bromide
isomerism? (en = ethylenediamine) [AIPMT-2005]
6. Which of the following is considered to be an anticancer
(1) Cis- [Pt(NH3)2Cl2]
species? [AIPMT-2004]
(2) Trans - [Co(en)2 Cl2] +
CH2 (3) Trans- [ Pt (NH3)2 Cl2]
Cl
(4) Cis - [Co(en)2 Cl2] +
Pt CH2
(1) 13. [Co(NH3] 4 (NO2)2] Cl exhibits [AIPMT-2006]
Cl Cl (1) linkage isomerism, geometrical isomerism and
optical isomerism
(2) linkage isomerism, ionisation isomerism and optical
Cl Cl
isomerism
Pt (3) linkage isomerism, ionisation isomerism and
(2)
Cl Cl geometrical isomerism
(4) ionisation isomerism, geometrical isomerism and
optical isomerism
H3N Cl
14. [Cr (H2O)6] Cl3 (at no. of Cr = 24) has a magnetic moment
Pt of 3.83 BM. the correct distribution of 3d electrons in
(3)
H3N Cl the chromium of the complex is [AIPMT-2006]
(1) 3d 1xy ,31yz ,3d z1 2

H3N Cl (2) 3d x 2 ,3d ,3d 1yz

1
 y2 z2
Pt (3) 3d xy ,3d( x ,3d 1yz
(4) 2
y2 )
H3N Cl
(4) 3d 1xy ,3d 1yz ,3d zx1
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Coordination Compounds 157

15. The d electron configurations of Cr2+, Mn2+, Fe2+ and Ni2+ 25. The complex, [Pt(Py)(NH3)BrCl] will have how many
are 3d4, 3d 5,3d6 respectively. Which one of the following geometrical isomers [AIPMT-2011]
aqua complexes will exhibit the minimum paramagetic (1) 4 (2) 0
behaviour (At. No of Cr = 24, Mn = 25, Fe = 26, Ni = 28) (3) 2 (4) 3
[AIPMT-2007]
26. The complex [Co(NH 3) 6] [Cr(CN) 6 ] and [Cr(NH 3) 6 ]
(1) [Fe(H2O)6] 2+ (2) [Ni(H2O)6] 2+ [Co(CN)6] are the examples of which type of isomerism?
(3) [Cr(H2O)6] 2+ (4) [Mn (H2O)6] 2+ (1) Ionisation isomerism [AIPMT-2011]
16. Which of the following will give a pair of enantiomers ? (2) Coordination isomerism
(en = NH2CH2CH2NH2) [AIPMT-2007]
(3) Geometrical isomerism
(1) [Cr (NH3)6] [Co(CN)6]
(4) Linkage isomerism
(2) [Co(en)2 Cl2]Cl
27. Of the following complex ions ions which is diamagnetic
(3) [Pt (NH3)4] [PtCl6]
in nature [AIPMT-2011]
(4) [Co(NH3)4 Cl2] NO2
(1) [Ni(CN)4] 2- (2) [CuCl4] 2-
17. Which of the following complexes exhibits the highest
(3) [COF6] 3- (4) [NiCl4] 2-
paramagnetic behaviour ? Where, gly = glycine, en =
ethylendiamine and bpy = bipyridyl moities 28. Which one of the follwoing is an outer orbital complex &
exhibits paramagenetic behaviour? [AIPMT-2012]
(1) [V(gly) 2(OH)2 (NH3)2] + [AIPMT-2008]
2+
(1) [Ni (NH3)6] 2+ (2) [Zn (NH3)6] 2+
(2) [Fe (en) (py) (NH3)2]
(3) [Cr(NH3)6] 3+ (4) [Co (NH3)6] 3+
(3) [Co(ox)2 (OH)2] –
29. A magnetic moment of 1.73 BM will be shown by one
(4) [Ti(NH3)6] 3+
among the following [AIPMT-2013]
18. In which of the following coordination entities the
(1) [Cu(NH3)4] 2+ (2) [Ni (CN)4] 2-
magnitude of   (CFSE in octahedral field) will be
maximum? [AIPMT-2008] (3) TiCl4 (4) [CoCl6] 4-
(1) [Co (H2O)6] 3+
(2) [Co (NH3)6] 3+ 30. Which of the following complexes is used to be as an
3– anticancer agent [AIPMT-2014]
(3) [Co (CN)6] (4) [Co (C2O4)3] 3–
(1) Mer - [Co(NH3)3Cl3]
19. Which of the following does not show optical isomerism?
[AIPMT-2009] (2) Cis- [Ptcl2(NH3)2]
(1) [Co(en)2 Cl2] +
(2) [Co(NH3)3 Cl3] 0 (3) Cis-K2 [PtCl2 Br2]
(3) [Co)en) Cl2 (NH3)2] +
(4) [Co(en)3] 3+ (4) Na2CoCl4
20. Which of the following does not show optical isomerism 31. Among the following complexes, the one which shows
? (en= ethylenediammine) [AIPMT-2009] zero crystal field stabilasation energy (CFSE) is
(1) [Sc(H2O)3 (NH3)3] 3+ (2) [Ti(en)2 (NH3)2] 4+ [AIPMT-2014]
3+
(3) [Cr (NH3)6] 3+ (4) (Zn(NH3)3+ (1) [Mn(H2O6] (2) [Fe(H2O6] 3+
2+
21. Out of TIF6 , CoF6 , Cu2Cl2 and NiCl42– (At. no. Z of
2– 3– (3) [Co(H2O6] (4) [Co(H2O6] 3+
Ti = 22, Co = 27, Cu = 29, Ni = 28) the colourless 32. The name of complex ion [Fe(CN6)] 3– is
species are [AIPMT-2009] (1) hexacyanoiron (III) ion [AIPMT-2015]
(1) TIF62– and CoF63– (2) Cu2Cl2 and NiCl42– (2) hexacyanitoferrate (III) ion
(3) TIF22– and Cu2Cl2 (4) CoF63– and NiC42– (3) tricyanoferrate (III) ion
22. The existence of two different coloured complexes with (4) hexacyanidoferrate (III) ion
the composition of [Co(NH3)4 Cl2] + is due to 33. The sum of coordination number and oxidation number
(1) linkage isomerism [AIPMT-2010] of the metal M in the complex [M(en)2 (C2O4)Cl (Where,
(2) geometrical isomerism en is ethylendediamine) is [AIPMT-2015]
(3) coordination isomerism (1) 9 (2) 6
(4) ionisation isomerism (3) 7 (4) 8
23. Crystel field stabilisation energey for high spin d 4 34. The hybridisation involved incomplex [Ni(CN) 4] 2- is
octahedral comple is [AIPMT-2010] (Atomic number of Ni = 28) [AIPMT-2015]
(1) –1.80 (2) –1.60 + P (1) dsp2 (2) sp3
(3) –1.20 (4) – 0.60 (3) d2sp2 (4) d2sp3
24. Which of the following comlex ions is not expected to 35. Number of possible isomers for the complex [Co(en)2 Cl
absorb visible light? [AIPMT-2010] will be (en ethylendiamine) [AIPMT-2015]
(1) [Ni (CN)4] 2- (2) [Cr (NH3)6] 3- (1) 2 (2) 1
(3) [Fe (H2O6)4] 2+ (4) [Ni (H2O6)4] 2+ (3) 3 (4) 4
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158 Coordination Compounds

36. Which of these statements about [Co(CN)6] 3– is ture ? 45. An example of a sigma bonded organometallic compound
(1) [Co(CN)6] 3- has no unpaired electrons and will be is [NEET-2017]
in a low-spin configuration. [AIPMT-2015] (1) ruthenocene
(2) [Co(CN)6] 3- has four unpaired electrons and willbe (2) Gignard’s reagent
ina low-spin configuration. (3) ferrocence
(3) [Co(CN)6] 3- has four unpaired electrons and will be (4) cobaltocene
in a low -spin configuration
46. The type of isomerism shown by the complex CoCl2 (en)2]
(D) [Co(CN)6] 3- has no unpaired electrons and will be is [NEET-2018]
in high -spin configuration.
(1) Ionization isomerism
37. Cobalt (III) chloride forms several octahedral complexes
(2) Coordination isomerism
with ammonia. Which of the following will not give test
for chloride ions with silver nitrate at 250C ? (3) Geometrical isomerism
[AIPMT-2015] (4) Linkage isomerism
(1) CoCl3. 3NH3 (2) CoCl3. 4NH3 47. The geometry and magnetic behaviour of the complex
(3) CoCl3.5NH3 (4) CoCl3. 6NH3 [Ni(CO)4 ] are [NEET-2018]
38. Jahn-Teller effectg is not observed in high spin complexes (1) square planar geometry and paramagnetic
of [NEET-2016] (2) tetrahedral geometry and diamagnetic
(1) d 7 (2) d8 (3) square planar geometry and diamagnetic
(3) 8 4 (4) d9 (4) tetrahedral geometry and paramagnetic
39. The correct increasin order of trans-effect of the following 48. Iron carbonyl, Fe(CO)5 is [NEET-2018]
species is [NEET-2016] (1) trinuclear (2) mononuclear
(1) NH3 > CN = > Br– > C6H5– (3) tetranuclear (4) dinuclear
(2) CN– > C6H5- > Br– NH3
49. What is the correct electronic configuration of the cen-
(3) Br– > CN– > NH3 > C6H5– tral atom in K4[Fe(CN)6] based on CFT [NEET-2019]
(4) CN– > Br- > C6H5 > NH3 4
(1) t2 g eg
2 6
(2) t2 g eg
0

40. Which of the follwing pairs of d-orbitals will have (3) e t23 3
(4) e t24 2
electrondensity along the axis ? [NEET-2016]
50. Which of the following is the correct order of increasing
(1) d z 2 , d xz (2) dxz, d yz
field strength of ligands to form coordination com-
(3) d 2, d (4) d xy , d x  y
2 2
pounds? [NEET-2020]
41. Which of the following has longest C — O bond length? – –
(1) SCN < F < CN < C2O4 – 2–
(Free C — O bond length in CO is 1.128A.)
(2) F– < SCN– < C2O42– < CN–
[NEET-2016]
– (3) CN– < C2O42– < SCN– < F–
(1) [Co(CO)4] (2) [Fe (CO)4] 2–
(3) [Mn(CO)6] +
(4) Ni (CO)4 (4) SCN– < F– < C2O42– < CN–
42. Pick out the correct statement with respect to [Mn(CN)6]3– 51. Match the coordination number and type of hybridisation
[NEET-2017] with distribution of hybrid orbitals in space based on
Valence bond theory.
(1) It is sp 3d2 hybridised and octahedral
Coordination No. Distribution of hybrid
(2) It is sp 3 d2 hybridised and tetrahedral
& type of hybri. orbitals in space
(3) It is d 2sp3 hybridised and octahedral
(a) 4, sp3 (i) trigonal
(4) It is dsp 2 hybridised and square planar
bipyramidal
43. Correct increasing order for the wavelengths of absorption
(b) 4, dsp2 (ii) octahedral
in the visible region for the complexes of CO3+ is
[NEET-2017] (c) 5, sp3d (iii) tetrahedral
(1) [Co(en)3] 3+ ,[Co(NH3)6] 3+ [Co(H2O6)] 3+ (d) 6, d2sp3 (iv) square planar
(2) [Co(H2O)6] 3+ ,[CO(en3)] ]3+, [Co(NH3)6] 3+ Select the correct option : [NEET-2020]
(3) [Co(H2O6)3] 3+ ,[Co(NH3)3+], [Co(NH3)6] 3+ (1) (a)-(ii) (b)-(iii) (c)-(iv) (d)-(i)
(4) [Co(NH3)6] 3+ ,[Co(en3)3+], [Co(H2O)6] 3+ (2) (a)-(iii) (b)-(iv) (c)-(i) (d)-(ii)
44. The correct order of the stoichiometrics of AgCl formed (3) (a)-(iv) (b)-(i) (c)-(ii) (d)-(iii)
when AgNO3 in excess is treated with the complexes : (4) (a)-(iii) (b)-(i) (c)-(iv) (d)-(ii)
CoCl3 6NH3 , CoCl3. 5NH3 . 4NH3 respectively is 52. Tritium, a radioactive isotope of hydrogen, emits which
(1) 1 AgCl, 3AgCl, 2AgCl [NEET-2017] of the following particles ? [NEET-2021]
(2) 3 AgCl, 1AgCl, 2AgCl (1) Beta ( –) (2) Alpha ()
(3) 3 AgCl, 2Agcl, 1AgCl (3) Gamma () (4) Neutron (n)
(4) 2 AgCl, 3AgCl, 1AgCl
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Coordination Compounds 159

53. Ethylene diaminetetraacetate (EDTA) ion is : 56. Given below are two statements : one is labelled as As-
(1) Hexadentate ligand with four "O" and two "N" sertion (A) and the other is labelled as Reason (R).
donor atoms [NEET-2021] [NEET-2022]
(2) Unidentate ligand Assertion (A): The metal carbon bond in metal carbonyls
(3) Bidentate ligand with two "N" donor atoms possesses both  and  character..
(4) Tridentate ligand with three "N" donor atoms Reason (R): The ligand to metal bond is a  bond and
54. Match List-I with List-II [NEET-2021] metal to ligand bond is a  bond.
List-I List-II In the light of the above statements, choose the most ap-
propriate answer from the options given below:
(a) [Fe(CN)6] 3– (i) 5.92 BM
(1) Both (A) and (R) are correct and (R) is the correct
(b) [Fe(H2O)6] 3+ (ii) 0 BM
explanation of (A)
(c) [Fe(CN)6] 4– (iii) 4.90 BM
2+
(2) Both (A) and (R) are correct but (R) is not the
(d) [Fe(H2O)6] (iv) 1.73 BM correct explanation of (A)
Choose the correct answer from the options given below: (3) (A) is correct but (R) is not correct.
(1) a–iv, b–ii, c–i, d–iii (2) a–ii, b–iv, c–iii, d–i (4) (A) is not correct but (R) is correct.
(3) a–i, b–iii, c–iv, d–ii (4) a–iv, b–i, c–ii, d–iii 57. The IUPAC name of the complex
55. Match List-I with List-II [NEET-2022] [Ag(H2O)2][Ag(CN)2] is: [NEET-2022]
List-I List-II (1) dicyanidosilver(I) diaquaargentate(I)
(Complexes) (Types) (2) diaquasilver(I) dicyanidoargentate(I)
(a) [Co(NH3) 5NO2]Cl2 (i) Ionisation (3) dicyanidosilver(II) diaquaargentate(II)
& [Co(NH3)5ONO]Cl2 isomerism (4) diaquasilver(II) dicyanidoargentate(II)
(b) [Cr(NH3)6] [Co(CN)6] (ii) Coordination 58. The order of energy absorbed which is responsible for
& [Cr(CN)6] [Co(NH3)6] isomerism the color of complexes [NEET-2022]
(c) [Co(NH3)5(SO4)]Br (iii) linkage (i) [Ni(H2O)2(en)2] 2+
& [Co(NH3)5Br]SO4 isomerism (ii) [Ni(H2O)4(en)] 2+ and
(d) [Cr(H2O)6]Cl3 & (iv) solvate (ii) [Ni(en)3] 2+ is
[Cr(H2O)5Cl]Cl2.H2O isomerism (1) (iii) > (i) > (ii)
Choose the correct answer from the options given below: (2) (ii) > (i) > (iii)
(1) a–iii, b–i, c–ii, d–iv (2) a–ii, b–iii, c–iv, d–i (3) (i) > (ii) > (iii)
(3) a–iii, b–ii, c–i, d–iv (4) a–iv, b–iii, c–ii, d–i (4) (iii) > (ii) > (i)
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160 Coordination Compounds

9.15
DAILY PRACTICE PROBLEM (DPP) – 01 MISCELLANEOUS QUESTIONS FROM NCERT
1. (1) 2. (3) 3. (2) 4. (4) 5. (4) 1. (2) 2. (2) 3. (4) 4. (1) 5. (3)
6. (3) 7. (2) 8. (3) 9. (4) 10. (3) 6. (1) 7. (2) 8. (3) 9. (1) 10. (1)
11. (1) 12. (2) 13. (2) 14. (1) 15. (1)
DAILY PRACTICE PROBLEM (DPP) – 02
16. (3) 17. (3) 18. (2) 19. (4) 20. (2)
11. (2) 12. (1) 13. (1) 14. (2) 15. (2) 21. (4) 22. (4) 23. (2) 24. (2) 25. (4)
16. (2) 17. (3) 18. (3) 19. (1) 20. (4) 26. (2) 27. (3) 28. (1) 29. (1) 30. (2)
21. (3) 22. (4) 23. (4) 24. (3) 25. (3) 31. (4) 32. (2) 33. (3) 34. (1) 35. (2)
36. (3) 37. (4) 38. (3) 39. (1) 40. (1)
DAILY PRACTICE PROBLEM (DPP) – 03
41. (2) 42. (3) 43. (3) 44. (2) 45. (3)
26. (2) 27. (4) 28. (2) 29. (4) 30. (2) 46. (2) 47. (4) 48. (2) 49. (4) 50. (3)
31. (2) 32. (1) 33. (1) 34. (3) 35. (4)
36. (2) 37. (1) 38. (2) 39. (3) 40. (2) NCERT EXEMPLAR OBJECTIVE TYPE QUESTIONS
1. (2) 2. (3) 3. (2) 4. (4) 5. (1)
DAILY PRACTICE PROBLEM (DPP) – 04
6. (3) 7. (1) 8. (3) 9. (1) 10. (4)
41. (4) 42. (2) 43. (4) 44. (1) 45. (1) 11. (1) 12. (2) 13. (2) 14. (3)
46. (4) 47. (2) 48. (3) 49. (4) 50. (2)
51. (1) 52. (3) 53. (2) 54. (2) 55. (1) ASSERTION–REASON & STATEMENT QUESTIONS
1. (3) 2. (1) 3. (1) 4. (1) 5. (1)
DAILY PRACTICE PROBLEM (DPP) – 05
6. (2) 7. (2) 8. (3) 9. (4) 10. (1)
56. (4) 57. (2) 58. (3) 59. (2) 60. (2) 11. (1) 12. (2) 13. (2) 14. (1) 15. (1)
61. (3) 62. (1) 63. (1) 64. (2) 65. (1)
66. (2) 67. (3) 68. (3) 69. (2) 70. (2) MATRIX TYPE QUESTIONS

DAILY PRACTICE PROBLEM (DPP) – 06 1. (1) 2 (3) 3. (1) 4. (2) 5. (2)

71. (3) 72. (3) 73. (3) 74. (4) 75. (1) ARCHIVE QUESTIONS
76. (1) 77. (1) 78. (1) 79. (3) 80. (2)
81. (1) 82. (3) 83. (4) 84. (4) 85. (3) 1. (2) 2. (2) 3. (3) 4. (4) 5. (4)
86. (4) 87. (2) 88. (1) 89. (4) 90. (3) 6. (3) 7. (1) 8. (2) 9. (2) 10. (2)
11. (3) 12. (4) 13. (3) 14. (4) 15. (2)
DAILY PRACTICE PROBLEM (DPP) – 07 16. (2) 17. (3) 18. (3) 19. (2) 20. (3)
21. (3) 22. (2) 23. (4) 24. (1) 25. (2)
91. (1) 92. (2) 93. (3) 94. (2) 95. (1)
96. (4) 97. (2) 98. (4) 99. (2) 100. (3) 26. (1) 27. (1) 28. (1) 29. (1) 30. (2)
101. (4) 102. (1) 103. (4) 104. (4) 105. (1) 31. (2) 32. (4) 33. (2) 34. (1) 35. (3)
36. (1) 37. (1) 38. (2) 39. (2) 40. (3)
DAILY PRACTICE PROBLEM (DPP) – 08 41. (2) 42. (3) 43. (1) 44. (3) 45. (2)
46. (3) 47. (2) 48. (2) 49. (2) 50. (4)
106. (4) 107. (2) 108. (4) 109. (2) 110. (1)
51. (2) 52. (1) 53. (1) 54. (4) 55. (3)
111. (2) 112. (3) 113. (4) 114. (4) 115. (2)
116. (2) 117. (2) 118. (1) 119. (4) 120. (2) 56. (3) 57. (2) 58. (1)