Coordination Compounds

CHAPTER
Coordination
20 Compounds
Chapter Highlights
Coordination compounds, Nomenclature, Isomerism, Bonding, Werner’s theory, Applications and Organometallic
compounds and various levels of multiple-choice questions.
COORDINATION COMPLEXES
When two or more saturated solutions of neutral com- TYPES OF COORDINATION COMPLEXES
pounds are mixed in stoichiometric proportion and left
undisturbed, a solid adduct is formed. These adducts or According to the stability of complexes, coordination com-
addition compound can be of two types: plexes are of two types:
Double salt It is formed by the combination of two salts.
Perfect or Penetrating Complex
• It retains its identity only in solid state but loses it in
solution. In a perfect complex, the complex ion is either completely
• On dissolution in water, it dissociates into original stable, that is, undissociated or is very feebly dissociated in
ions, for example, solution. For example,
+ –
K2SO4.Al2(SO4)3.24H2O(s) + aq 2K+(aq) + K4[Fe(CN)6] 4K + [Fe(CN)6]4
Feebly dissociated
Potash alum 2Al3+(aq) + 4SO42–
(aq) + 24H2O (l) –
Fe2+ + 6CN
FeSO4. (NH4)2SO4.6H2O(s) + aq Fe2+(aq) +
Mohr salt 2NH4 (aq) + 2SO42–
+
Imperfect or Normal Complex
(aq) + 6H2O (l)
In an imperfect complex, the complex ion is either less
Coordination complex It retains its identity not only in stable or dissociates appreciably.
solid state but also in solution. For example,
+ –
• It gives complex or different ions on dissociation. K2[Cd(CN)4] 2K + [Cd(CN)4]2
Appreciably dissociated
Fe(CN)2 (aq) + 4KCN(aq) K4[Fe(CN)6] (aq)
4K+ (aq) + [Fe(CN)6]4– (aq)
Cd2+ + 4CN –
A complex ion is defined as an electrically charged radical,
which is formed on combination of a simple cation with REPRESENTATION OF A COORDINATE
one or more simple ions or neutral molecules having COMPLEX
two constituents an acceptor (central metal atom) and a
donor (ligand). • A coordinate complex is represented as:
AX [M (K)a (L)b] BY
20.2 Chapter 20
• Here A and B are cationic and anionic species which Tridentate ligands
are ionizable and precipitable. These have three electron pairs to donate. For exvample,
• M is central metal atom like Cr, Mn, Fe, Co or Ni. 1. H2N (CH2)2 NH (CH2)2 NH2
• K and L are ligands that are electron pair donor species, Diethylenetriammine (dien)
which are non-ionizable and non-precipitable in
nature. 2. Terpyridyl (terpy) N N
• Sum of a and b is equal to the coordination number. N
• [ ] represents coordination sphere.
TERMS RELATED TO A COMPLEX

FA C T S TO R E M E M B E R
Coordination Sphere
The central metal atom and ligands directly attached to the  The attachment of a symmetrical bidentate ligand to the
metal atom collectively constitute the coordination sphere central metal atom is shown by a curve, where L is the
abbreviation of the symmetrical bidentate ligand and two
and are written in a square bracket [ ]. The atoms, ions or
‘A’ are two (similar) donor atoms.
molecules in this sphere are non-ionizable. A
For example, phen L
Central Metal Atom or Ion or Centre of A
Coordination  The attachment of an unsymmetrical bidetate ligand to
the central metal atom is shown by a curve where L is the
The central metal atom or ion to which one or more neu- abbreviation of the ligand and A and B are two (different)
tral molecules or ions are attached is called the centre of donor atoms. A
coordination. For example, glycinato (gly– ) L
B
Ligand
• The molecules and ions that surround the metal ion Tetradentate ligands
in a complex are known as ligands or complexing These have four electron pairs to donate. For example,
agents. 1. H2N (CH2)2 NH (CH2)2 NH (CH2)2 NH2
• An atom or group of atoms which bind to the central
metal atom or ion through lone pair of electrons pres- Triethylenetetraamine or trien
ent on its donor atom. 2. Triaminotriethylamine or tren
−
• Depending on number of pairs donated by different CH2COO
atoms, it is of following types: 3. Nitriloacetato :N CH2COO
−
−
CH2COO
Unidentate ligands
– Pentadentate ligands
These have one electron pair to donate. For example, X ,
–
NH2, CN , OH
– These have five electron pairs to donate. For example,
Ethylene diamminetri acetate
Bidentate ligands CH2 –N (CH2COO–)2
These have two electron pairs to donate. For example, •
1. C2O4–2 (Oxalato) CH2–NH (CH2COO–)
2. H2NCH2COO– (Glycinato)
Hexadentate ligands
3. H2NCH2CH2NH2 or en (Ethylenediammine)
These have six electron pairs to donate. For example,
N N Ethylenediamminetetra acetate (EDTA)
4. Bipyridyl (bipy)
CH2–N (CH2 COO–)2
•
CH2–N (CH2COO–)2
N N
5. 1, 10-phenanthroline (phen) Chelating ligands
When a polydentate ligand binds to the central metal atom
by more than one donor site, a cyclic ring like structure
Coordination Compounds 20.3
known as a chelate is formed and this ligand is called a Coordination Number or Ligancy
chelating ligand.
The total number of ligands surrounding the central metal
H2C NH2 NH2 CH2 atom in the coordination sphere is called its co-ordination
number.
Pt
For example, [Ni (CN)4]–2
H2C NH2 NH2 CH2 Here, coordination number is 4.
Figure 20.1 Structure of a chelating ligends K4[Fe(CN)6]
• Such a cyclic or a chelate complex is more stable Here, coordination number is 6.
than an open complex due to the chelating effect [Fe (C2O4)3 ]–3
–2
or macro-cyclic effect. For example, in case of [Ni Here, coordination number is 6 since C2O4 is bidentate in
(en)3]2+, stability is nearly 1010 times more than nature.
[Ni(NH3)6]2+.
Sidgwick theory of complexes
FA C T S TO R E M E M B E R • Transition metal or ions are Lewis acids.
• Ligands are electron donor species that is, Lewis
 Chelates are used in softening of hard water and in the
bases.
separation of lanthanides and actinides.
 Chelating agents are used in medicine to remove metal
• Transition metal ions can form complex compounds
ions like Hg2+, Pb2+ and Cd2+. For example, EDTA is used by accepting lone pair of electrons from ligands.
to remove lead and hence, prevent lead poisoning. • The bond formed between the transition metal ion
and the ligand is a coordinate covalent bond
(L M Here, L = Ligand, M = Central
Ambidentate ligands
metal atom).
Such ligands have two or more donor sites, however,
• Transition metal ion must contain vacant orbitals
during complex formation only one donor site is used. For
to accept the electron pairs from ligands.
example, .. .. .. ..
__
.. __ .. • Ligands should contain at least one lone pair of
.. N = O: and :O
:O← .. − N = O: electrons to donate.
Nitro group (I) Nitrito group (II)
__ .. .. Effective Atomic Number (EAN)
:C≡ N and :C ← N:
Cyano group (I) Isocyano group (II) • It was introduced by Sidgwick who defined it as,
SCN and NCS “Effective atomic number is the total number of elec-
Thiocyanide Isothiocyanide trons present around central metal ion in a complex.”
EAN = [Atomic number of the metal]–[Number of
electrons lost in the formation of its ion] + [Number
FA C T S TO R E M E M B E R of electrons gained from ligands].
That is, EAN = Z–Oxidation number + 2 × Number
2–
Thiosulphato (S2O3 ) can also act as an ambidentate
–
of ligands. (Number of electrons gained from ligand)
– –
ligand, that is, (O––S2O2 ) ion and (S –SO3 ) ion. • Sidgwick proposed that metal ion is stable if its EAN
is equal to the atomic number of the nearest inert gas.
For example, in K4[Fe(CN)6]
Flexidentate ligands
EAN = 26 – 2 + 12
Here, the ligand has many donor sites, however, not all of
= 36
them are essentially used in all cases. For example, EDTA
• In some complexes, the EAN is not equal to the
it often acts as a penta coordinate ligand, leaving one of the
atomic number of the nearest inert gas.
acetate group dangling free.
For example, in K3[Fe(CN)6]
π-acid ligands EAN = 26 – 3 + 12 = 35
Such ligands are capable of accepting an appreciable In [Ni(CN)4]2–
amount of π electron density from the central metal atom
into their empty π or π* orbitals. For example, CO. EAN = 28 – 2 + 8 = 34
20.4 Chapter 20
Table 20.1 Effective Atomic Numbers

It means that higher the stability of the complex, higher
Electrons Electrons 2–
is the value of K for it. For example, for [Cu(CN)4] ,
lost in ion gained from
3–
Complex formation ligands EAN K = 2 × 1027 and for [Fe(CN)6] , K = 7.7 × 1043
[Ni(CO)4] 0 8 28 – 0 + 8 = 36 • Stability ∝ Charge on cation or oxidation number
1
Stability ∝ __________
3–
[Cu(CN)4] 1 8 29 – 1 + 8 = 36
Size of cation
[Ag(NH3)]4+ 1 8 47 – 1 + 8 = 54
Cations with higher charge and smaller size form
4–
[Co(CN)6] 2 12 27 – 2 + 12 = 37 more stable complexes. For example, Fe3+ forms
[Ni(NH3)6]2+ 2 12 28 – 2 + 12 = 38 more stable complex then Fe2+.
• Stability ∝ Basic nature of ligands or electron
2–
[PdCl4] 2 8 46 – 2 + 8 = 52
[Pt(NH3)2 Br2] 2 8 78 – 2 + 8 = 84 density
[Ni(py)(en) 2 12 28 – 2 + 12 = 38 For example, cyano, amine complex >
[(NH3)3]2+ X-complexes more basic ligands
• Stability ∝ Number of chelate rings (macro cyclic
effect)
PREPARATION OF COMPLEXES
Complexes are mainly prepared by following methods: FA C T S TO R E M E M B E R
By Substitution Reactions Complex formation tendency of some divalent cations
decrease as shown: Cu2+ > Ni2+ > Co2+ > Fe2+ > Mn2+
[Cu(H2O)4] SO4 + 4NH3 [Cu(NH3)4] SO4 + 4H2O
[Co(NO2)6] + 2NH2–CH2–CH2–NH2
–3
NOMENCLATURE OF COORDINATION
[Co (en)2 (NO2)2]+ + 4NO2 COMPOUNDS
By Direct Combinations The basic rules are as follows:
• While naming salts, the positive ion (cation) is
NiCl2 + 6NH3 [Ni (NH3)6 ]Cl2 named first, followed by the negative ion (anion).
CoCl3 + 6NH3 [Co (NH3)6] Cl3 For example, in [Co(NH)5 Br] Br2, the name is first
assigned to [Co(NH3)5 Br]2+ and then to Br– .
PtCl4 + 2KCl K2 [PtCl6] • Name of the non-ionic or neutral complex must be
written in one word.
By Redox Reactions • Within a complex species, the ligands are named
CoCl2 + 2NH4Cl + 10 NH3 + H2O2 before the metal atom.
• Names of the neutral ligands are written as it is.
2[Co (NH3)6] Cl3+ 2H2O Some exceptions are:
H2O – aqua
2[Co (H2O)6] (NO3)2+ 8NH3+ 2NH4NO3+ H2O2
NH3 – ammine
2[Co (NO3)2 (NH3)5] (NO3)2 + 14 H2O
CO – carbonyl
NO – nitrosyl
CS – thiocarbonyl
Stability of complexes NS – thionitrosyl
The stability of a complex depends upon the following • Names of the negative ligands end with ‘O’,
factors: as in the case of:
Stability ∝ K (Stability constant)
– + Cl– – chloro or chlorido
Ma+ + nLx (MLn)b
(MLn)b+ CH3COO– – acetato
K = _______
[M+a] [L]n CO32– – carbanato
C2O42 – oxalato • If the complex ion is positive, then the name of metal
NO2– – nitro ion is written as it is. For example, [Cr(en)3]Cl3 is
NO3– – nitrato named as trisethylenediaminecobalt(III) bromide.
S2– – sulphido • If the complex ion is an anion and symbol of the
metal is taken from latin language, their names in the
SO42– – sulphato
complex is also derived from latin.
NH2– – amine or amino
For example,
NH2– – imido
Ferrum – ferrate
OH – – hydroxo
Argentum – argenate
O22 – peroxo
Stannum – stannate
• The names of the positive ligands end with ‘ium’, Therefore, K4 [Fe(CN)6] becomes Potassium
like for example, hexacyanoferrate(II).
H3O+ – hydronium • Molecule of water of crystallization are indicated
NO2+ – nitronium after the name of the complex. Arabic numerals are
used to indicate the number of such molecules.
N2H5+ – hydrazinium
For example, Al K(SO4)2.12H2O is named as
• If the same complex compound contains different
aluminium potassium sulphate 12-water
ligands, their names are written in alphabetical order.
• Geometrical isomers are named by using the prefixes
• Prefixes like di, tri, tetra, penta, ………. are used
‘cis’ for adjacent (90° apart) positions and ‘trans’ for
before the ligands, to mention their numbers.
opposite (180° apart) positions before the name of
• The number of complex ligands like bidentate and the ligands.
tridentate is mentioned with bis, tris, tetrakis if they
• In square planar complexes, the groups at positions
already contain di, tri, in their names.
(1, 2) and (3, 4) are cis to each other, while those at
• While naming the ambidentate ligands, the ligands positions (1, 3) and (2, 4) are trans to each other.
are named after the point of attachment.
For example, For example,
SCN–, S-thiocyanato (here S is donor) [4] H N Cl [1]
3
NCS–, N-isothiocyanato (here N is donor)
• If the complex contains two or more metal atoms, the Pt
bridging ligands are indicated by prefix μ, before the
names of such ligands, as in the case of [3] Cl NH3 [2]
[(NH3)5 Cr – OH – Cr(NH3)5]Cl5 Trans-diamminedichloroplatinum (II)
Pentaamminechromium (III)-μ hydroxopentaaminech-
romium(III) chloride [4]
H3N Cl [1]
3+ Pt
NH
H 3N Cl [2]
(en)2Fe Fe(en)2 [3]
Cis-diamminedichloroplatinum(II)
OH
• In mono nuclear octahedral complexes of Ma4b2 type
Bis(ethylenediamine)cobalt(III)-μ-hydroxo-μ-imido (1, 2), (1, 3), (1, 4), (1, 5), (6, 2), (6, 3), (6, 4), (6, 5),
bis(ethylenediamine)cobalt(III) (2, 3), (3, 4) and (5, 2) are cis positions while (1, 6),
or (2, 4) and (3, 5) are trans-positions.
Tetrakis(ethylenediamine)-μ-hydroxo-μ-imidodicobalt • In mono nuclear complexes of Ma3b3 type 1, 2, 5 are
(III) ion. cis while 1, 2, 6 are trans-positions.
• The oxidation number of the central metal ion should • Dextro and leavo rotatory optically active compounds
be mentioned in roman numerals in the parenthesis are designated by (+) and (–) or d- and l- respectively.
immediately after the name of the metal ion. It can be shown in the following example:
20.6 Chapter 20
(+) or d-K3[Ir (C2O4)3] is potassium (+) or d-trioxa- [Cr(en)3]Cl3 d or l tris(ethylenediamine)

lato iridate(III). chromium(III) chloride
[CoCl2 ((NH2)2CO)2] dichlorobis(urea)cobalt(II)
Compounds and their IUPAC names Fe(C5H5)2 bis(cyclopentadienyl)iron(II)
[Fe(C2H5N)2] dipyridineiron(0)
Complex cations
K3[Cr(CN)6] potassium hexacyanochro- Cationic as well as anionic Complexes [ ]n+ [ ]n–
mate(III) [Pt (NH3)4 Cl2][Pt Cl4]
IV II
tetraaminedichloro plati-
[Ti(H2O)6]Cl3 hexaaquatitanium(III) chlo- num(IV) tetrachloro
ride palatinate(II)
[Cr(NH3)6]Cl3 hexaamminechromium(III) [Pt(py)4] [PtClt] tetrapyridineplatinum(II)
chloride tetrachloroplatinate(II)
[CrSO4(NH3)4]NO3 tetraamminesulphatochro- [Pt(py)4][PtCl4] tetrapyridineplatinum(II)
mium (III) nitrate tetrachloroplatinate(II)
[Co(en)2 F2]ClO4 bis-(ethylenediamine) di-
fluorocobalt(III) perchlorate Bridging groups
[Cu(acac)2] bis(acetylacetonato)cop- [Be2O(CH3COO)6] hexa-μ-acetato(O,O’)-μ4–
per(II) oxo-tetraberylium(II)
[CoCl–CN–NO2–(NH3)3] triamminechlorocyanonitro- [(CO)3Fe(CO)3Fe(CO)3] tri-μ-carbonyl-bis
cobalt (III) [tricarbonyl iron(0)]
–
[Pt(NH3)4(NO2)Cl]SO4 tetraamminechloronitro- [(NH3)5Co NH2.Co(NH3)5](NO3)5
platinum(IV) sulphate μ-amidobis [pentaammine cobalt(III)] nitrate
[Cr(NO2)3 (NH3)3] triamminenitrochromium(III)
[Co(en)2 Cl(ONO)]+ chlorobis(ethylenediamine) (C6H5)3 P Cl
Cl Cl
Cl
nitrocobalt(III) ion
Pd Pd
Complex anions Cl Cl P(C6H5)3
–
[Pt(NH3)4 (ONO)Cl]2 tetraamminechloronitritopa- Chlorotriphenylphospine palladium(II)-μ-dichloro- chlo-
latinate(IV) ion rotriphenyl palladium(II)
K2[Cr(CN)2O2(O2)NH3] potassium amminedicyano
or
dioxoperoxochromate(VI)
transbis – μ-chlorido chlorido triphenyl phosphine pal-
Na[ZnCl4] sodium tetrachlorozin-
ladium (II)
cate(II)
(NH4)3[Co(C2O4)3] ammoniumtris-(oxalato)- ISOMERISM IN COORDINATION
tcobaltate(III) COMPOUNDS
–
cis-[PtBrCl(NO2)2]2 cis-bromochloronitropalati-
nate (II) ion Compounds that have same chemical formula but different
Na3[Ag(S2O3)2] sodium bis (thiosulphato) structural arrangements are called isomers. Isomerism is of
argentate(I) two types: structural and stereo isomerism.
K2[OsCl5N] potassium pentachloronitri-
do osmate(VI) Structural Isomerism
Na3 [Ag(S2O3)12] sodium bis-(thiosulphato) Ionization isomerism
argenate(I)
K3[Fe(CN)5NO] potassium pentacyanoni- Compounds that are composed of same elements having
trosyl ferrate(II) same composition but give different ions in solution are
K2[OSCl5N] potassium tetrafluoro borate called ionization isomers.
(V) 1. Ionization isomers are formed by the interchange of the
position of ligands inside and outside the co-ordination
Neutral complexes sphere.
[Cr(C6H6)2] bis(benzene)chromium(0) 2. Ionization isomers can be detected by conductance mea-
[Ni(CO)4] tetracarbonyl nickel(0) surements or by chemical tests.
For example,
(a) [Co(NH3)5 SO4]Br Red colour For example,

[Co(NH3)5 Br]SO4 Violet colour [Pt (NH3)2 Cl2], [Pt (NH3)4] [PtCl4]
In these isomers Br- and SO42– are the precipitable Ligand isomerism
ions, respectively. Consider the following two ligands:
(b) In the case of [Pt (NH3)4 Br2 ] Cl2 and [Pt (NH3)4 H2C–CH2–CH2 and H2C–CH–CH3
Cl2] Br2, Cl– and Br– are the precipitable ions, • • • •
respectively. H2N NH2 NH2 NH2
Hydrate isomerism 1, 3-diaminopropane(tn) 1, 2-diaminopropane(pn)
In these complex molecules there is difference in the posi- When such ligands form complexes, ligand isomerism
tion of water molecules, that is, in the number of water is observed.
molecules in the coordination sphere. [Co(tn)2 Cl2]+ and [Co (pn)2 Cl2]+ is another example in
this category.
For example CrCl3.6H2O has 3 isomers
[Cr(H2O)6]Cl3 violet Valency isomerism
[Cr(H2O)5]Cl2 H2O green It arises when the ligand is held by different type of valence
bonds, sometimes primary and sometimes secondary. See
[Cr(H2O)4]Cl 2H2O dark green the example below:
Here a fourth isomer [CrCl3 (H2O)3].3H2O also exists
O2
CoCl3(H2O)6 has 3 isomers which are,
(en)2Co Co(en)2 X4
1. [Co(H2O)6]Cl3
2. [CoCl2(H2O)4]Cl 2H2O NH2
3. [CoCl3(H2O)3] 3H2O and
Linkage isomerism O2
This isomerism is observed in ligands that have more than (en)2Co NH Co(en)2 X3
a single atom which can act as a donor, which is similar to
the case of an ambidentate ligand. For example, CN, NC; HX
SCN, NCS; NO2, ONO; Figure 20.2 Structures Depicting Valency Isomerism
[(NH3)5 CoONO]Cl2 Red colour
Coordination position isomerism
[(NH3)5 CoNO2]Cl2 Yellow colour
It arises in polynuclear complexes due to interchange of
[Cr(NH3)5 (SCN)] Cl2; [Cr(NH3)5 (NCS)]Cl2 ligands between the metal atoms as shown below:
Coordination isomerism OH
This isomerism occurs when the compounds contain both
(NH3)4Co Co(NH3)2Cl2 Cl2
cationic and anionic complexes and there is an exchange of
ligands between these complexes. NH2
For example, Unsymmetrical
1. [Cr(NH3)6][Co(CN)6] and [Cr(CN)6] [Co(NH3)6]
2. [Cu(NH3)4] [PtCl4] and [Cu(NH3)3 Cl] [Pt(NH3) Cl3]
OH
Polymerization isomerism Cl2
Cl(NH3)3Co Co(NH3)3Cl
It is used to describe those compounds which have the
same stoichiometric composition, but their molecular NH2
compositions are multiples of the simplest stoichiometric Symmetrical
arrangements. Figure 20.3 Structures Depicting Coordination Position Isomerism
20.8 Chapter 20
Stereo Isomerism • Mabcd type square planar complexes exists in three

isomeric forms.
Stereo isomerism arises when the isomers differ in the
arrangement of the atoms or groups in space. It is of two 1 3
types geometrical isomerism and optical isomerism.
M
Geometrical isomerism
It arises when exchange of atoms or groups or ions within the
2 4
coordination sphere of the complex changes the geometry. Figure 20.6 Trans Structure in Mabcd Type
• In geometrical isomers, when two identical ligands are
present in adjacent positions, it is called cis-isomerism In square planar complexes positions 1, 4 and 2, 3 are
and when such ligands are present diagonal (opposite) cis while 1, 3 and 2, 4 are trans. For example,
to each other, it is called trans-isomerism. [Pt(NH3)(Py)(Cl)(Br)]
• Complexes in which the coordination number of cen- • Octahedral complexes of the type Ma6 , Ma5b, or Mab5 ,
tral metal ion is 2, 3 or 4 (having tetrahedral struc- M(aa)3 do not exhibit geometrical isomerism.
ture) they do not exhibit geometrical isomerism.
• Octahedral complexes of the type Ma4b2, Ma4bc,
• Complexes in which the coordination number of cen-
Ma3b3,Ma2b2c2 etc. exhibit geometrical isomerism.
tral metal ion is 4 and have square planar structure,
they will exhibit geometrical isomerism. 1
1
• Square planar complexes of the type Ma4, Ma3b, Mab3, 5 2
M(aa)2 do not exhibit geometrical isomerism.
• Ma2b2, Ma2bc, M(aa)b2 or ab and Mabcd type square M
planar complexes exhibit geometrical isomerism.
For example, [Pt (NH3)2Br2] and [Pt(NH3)2 (Cl) (Br)] 4 3
6
6
H3N Br
Figure 20.7 Structure of Octahedral Complexes
Pt In octahedral complexes positions 1, 6; 2, 4 and 3, 5
+
H3N Br are trans positions, as in [Co(NH3)4Cl2]
cis
• Complexes of the type [M(aa)x2y2] can show
H3N Br geometrical (cis and trans) isomerism. For example,
Pt [Co(en)(NH3)2Cl2]+exhibits cis and trans isomerism.
Br NH33
NH NH3 + NH3 +
trans
Figure 20.4 [Pt (NH3)2Br2] Exhibitting Geometrical Isomerism H3N Cl
For example, [Pt (gly)2 ] Co en Co en
NH2 NH2 Cl Cl
H2C Pt CH2 Cl NH3

COO cis trans
trans
COO
cis Figure 20.8 Geometrical Isomerism in [M (aa) x2y2] type complexes
• Octahedral complexes of the type M(aa)2b 2,

COO NH2 where (aa) is a symmetric bidentate ligand, also
exhibits geometrical isomerism. For example,
H2C Pt CH2
[Co(en)2Cl 2]+
NH2 COO • Octahedral complex of the type [M(abcdef)] has 15
trans
different geometrical isomers with a pair of enantio-
Figure 20.5 Geometrical Isomers of [Pt(gly)2]
mers, as in [Pt(py)(NH3)(C1)(Br)(I)(NO2)]
Optical isomerism For example, [Co (en)3]3+

Complexes which do not contain any centre of symmetry Mirror
or plane of symmetry or axis of symmetry exhibit optical plane
isomerism. en 3+ en 3+
• Complexes with coordination number four, hav- en
ing tetrahedral structure can exhibit optical isom- Co3+
erism when all the four ligands are of different en Co3+
types.
Figure 20.11 Optical isomers of [Co(en)3]3+ ion
• Compound of type Ma2x2y2, Ma2x2yz, Ma2xyzl, en en
Mabcxyz, M(aa)3, M(aa)2x2 show optical isomerism.
d-form l-form
• Octahedral complexes of the type Ma2b2c2 type can
exist as two optical isomers.
[Mabcd] type Complexes
For example, [Pt (NH3)2 (Py)2 Cl2 ]+2 exhibits optical This type of complex ion/compound should exhibit
isomerism. optical activity. However, it has not been possible to
isolate optically active d-and l-forms of such a complex
Mirror plane due to their labile nature. For example, [As(CH3) (C2H5)
+2 +2 (S)(C6H5COO)]2+ ion. Since it does not possess a plane
Py Py
of symmetry, it is optically active.
Cl Py Py Cl
Co Co BONDING IN COMPLEXES
Cl NH3 H 3N Cl
Werner’s Theory
NH3 NH3 Central metal atom shows two types of valencies in coor-
dination compounds that is, primary (principal), secondary
Figure 20.9 [Pt (NH3)2 (Py)2 Cl2 ] Exhibitting Optical
+2
(auxillary valency) and the metal atom tries to satisfy both
its valencies.
• In the octahedral complexes of the type M(aa)2b2 the
cis isomer exists in two optical isomers. In case of Primary valency
trans isomer, optical isomerism is not possible.
Primary valency represents oxidation number of the central
For example, [Co (en)2 Cl2]+ metal atom.
Mirror plane
• Primary valency is always satisfied by anions.
For example, [Co (NH3)4 Cl2] Cl, [Co (NH3)5 Cl] Cl3,
en + en +
[Co (NH3)6]Cl3. Here, primary valency is 3 and it is
Cl Cl
satisfied by 3Cl– ions.
Co3+ Co3+ • Primary valency is written outside the coordination
sphere, but if species showing primary valency is
Cl Cl also showing secondary valency, it is also written
en en inside the coordination sphere.
Cis-d-isomer Cis-l-isomer
• Primary valency present outside the coordination
Figure 20.10 Optical isomer of [Co(en)2Cl2]+ ion
sphere is non-directional.
• Primary valency does not give the idea of geometry
• M(aa)3 type octahedral complexes also exists in two
of the coordination compounds.
optical isomers.
20.10 Chapter 20
Secondary valency Valence Bond Theory

Secondary valency represents coordination number of the To explain bonding in complex compounds, Linus Pauling
central metal atom. proposed the valence bond theory. Its main postulates are
• Secondary valency is satisfied by ligands (anions and as follows:
neutral molecules). For example, in K4[Fe(CN)6], the Postulates for valance bond theory
secondary valency of Fe is 6 and it is satisfied by 6
CN ligands. • The central atom loses a requisite number of electrons
to form the cation. The number of electrons lost is equal
In [Co (NH3)6] Cl3, the secondary valency of Co is 6 and it to the oxidation number of the resulting cation.
is satisfied by 6 NH3 molecules.
• The central cation makes available a number of empty
In [Co (NH3)5 Cl] Cl2, Co has a secondary valency 6 and it
orbitals which are equal to its coordination number
is satisfied by 5 NH3 and Cl– ion molecule.
and hence form dative bonds with the ligands.
• Secondary valencies are written inside the coordina-
tion sphere, as in [Co (NH3)5 Cl] Cl2 and [Co (NH3)4 • The cation orbitals hybridize to form new sets of
Cl2] Cl equivalent hybrid orbitals with definite directional
• Secondary valency is directional in nature. characteristics.
• Secondary valency gives a definite geometry to coor-
dination compounds. Table 20.2 Features of Complexes According to
VBT
Secondary valency is 2 for linear, 3 for trigonal planar,
4 for square planar or tetrahedral and 6 for octahedral. Co-ordination Type of Molecular Examples
Complexes, for example [Co (NH3)6 ]Cl3,[Co (NH3)5 Cl] number hybrid- geometry
Cl2 and [Co (NH3)4 Cl2] Cl will have octahedral shape. ization
• Secondary valency cannot be obtained in free state 1 sp Linear [CuCl2],

[Cu(NH3)2]+,
by the ionization of aqueous solution of coordination
[Ag(NH3)2]+
compounds. For example,
2 sp2 Trigonal [CuCl (Co)2]
[Co (NH3)4 Cl2] Cl [Co (NH3)4 Cl2]+ Cl– planar
• Secondary valency is denoted by thick (⎯) lines.
3 sp3 Tetrahedral [Ni(CO)4],
• Primary valency satisfying species can be obtained 2–
[NiCl4] ,
–
in free state by ionization of aqueous solution of [Cu(CN)4]3
coordination compounds. 4 dsp2 Square [Ni(CN)4] ,
2–
[Co (NH3)5 Cl] Cl2 + AgNO3 Here, 2 moles planar [PdCl4] ,

2–
of AgCl are precipated as follows: [Cu(NH3)4] ,

2+
2Cl– + 2Ag+ 2AgCl [Pt(NH3)4]

2+
White ppt.
5 sp3d or Trigonal [Fe(CO)5],
• Primary valency is shown by dotted (------) lines. dsp3 bipyramidal [CuCl5]3 ,
–
For example, [Ni(CN)5]

3–
,
3–
NH3 6 sp3d2 or Octahedral [Fe(CN)6] ,
H3N Cl d2sp3 [Ti(H2O)6] ,
3+
NH3 [Fe(CN)6] ,
4–
Cl Co 3–
NH3
[Co(NO2)6] ,
– 3–
[CoF6] 3,[FeF6] ,
H3N Cl
[Fe+ (NO+)
NH3
(H2O)5]2+,
2+
Figure 20.12 [Co(NH)6 ]Cl3 Depicting Both Primary and Secondary [Ni(NH3)6]
Valency
• The non bonding metal electrons occupy the inner d • The complexes formed by the involvement of nd
orbitals and do not participate in the hybridization. orbitals in hybridization are called outer orbital com-
• If the ligands are strong like CN–, CO, NH3 then the plexes or high spin complexes.
d electrons are rearranged, vacating some d orbitals • Each ligand contains a lone pair of electrons. A
(when the number of d-electrons are more than 3 dative bond is formed by the overlaping of a vacant
only) which can participate in hybridization. hybrid orbital of metal ion with a filled orbital of
•
– –
If the ligands are weak like F , Cl and H2O, the d the ligand.
electrons are not rearranged. • The complex will be paramagnetic if any unpaired
• The d orbitals involved in the hybridization may be electrons are present, otherwise it will diamagnetic.
either (n–1)d orbitals or outer nd orbitals. • The number of unpaired electrons in a complex gives
• The complexes formed by the involvement of (n–1)d the geometry of the complex and vice versa.
orbitals in hybridization are called inner orbital com-
plexes or low spin complexes.
Table 20.3 Physical Properties of Ammine Complexes

–
Molecular Colour No. of Cl ion Molar conductance No. of ions Structural formula
formula ppt. by AgNO3 ohm–1 cm2 mol–1
CoCl3 ammine complexes
1 CoCl3.6NH3 Orange 3 430 4 [Co(NH3)6]Cl3
CoCl3.5NH3.
2 Pink 3 430 4 [Co(NH3)5 H2O]Cl3
H2O
3 CoCl3.5NH3 Violet 2 250 3 [Co(NH3)5 Cl]Cl2
Green or
4 CoCl3.4NH3 1 100 2 [Co(NH3)4 Cl2]Cl
violet
5 CoCl3.3NH3 Blue-green 0 0 – [Co(NH3)3 Cl3]
PtCl4 ammine complexes
1 PtCl4.6NH3 4 520 5 [Pt(NH3)6]Cl4
2 PtCl4.5NH3 3 410 4 [Pt(NH3)5 Cl]Cl3
3 PtCl4.4NH3 2 240 3 [Pt(NH3)4 Cl2]Cl2

4 PtCl4.3NH3 1 100 2 [Pt(NH3)3 Cl3]Cl
5 PtCl4.2NH3 0 0 – [Pt(NH3)2 Cl4]

20.12 Chapter 20
Table 20.4 Differences Between Inner and Outer (vi) Octahedral shape of [Fe(CN)6]4– ion is given as:
Orbital Octahedral Complexes 4–
CN
Inner orbital octahedral Outer orbital octahedral CN CN
complexes complexes
These are formed by dsp2, These are formed
Fe
2
d sp3 type of hybridization. by sp3, sp3d2 type of
hybridization. CN CN
CN
These complexes have less These complexes
number of unpaired electrons, have greater number Figure 20.13 Structure of [Fe(CN)6]4– Ion
therefore, show low magnetic of unpaired electrons,
(vii) It has no unpaired electron, that is, n = 0, μ = 0
moment or no magnetic therefore, show high
hence it is diamagnetic.
moment. magnetic moment.
These are less reactive, These are more reactive, • K3[Fe(CN)6] or Hexacyanoferrate(III) ion,
therefore, substitution of therefore, substitution of [Fe(CN)6]3– : Formation of [Fe(CN)6]3– complex ion
ligands is fairly difficult. ligands is easy. by valence bond method can be shown as follows:
(i) Fe atom
These are formed by strong These are formed by
ligands. weak ligands. 3d 4s 4p
↑↓ ↑ ↑ ↑ ↑ ↑↓
(ii) Fe3+ ion
Structures and shapes of complexes on the basis of 3d 4s 4p
valence bond theory
↑ ↑ ↑ ↑ ↑
• K4[Fe(CN)6] or hexacyanoferrate(II) ion
(iii) Fe3+ ion under the influence of strong CN– ligands
[Fe(CN)6]4–: The formation of [Fe(CN)6]4– complex
3d 4s 4p
ion by valence bond method can be shown as follows:
↑↓ ↑↓ ↑
(i) Fe atom
3d 4s 4p (iv) d2sp3 hybrid orbitals of Fe3+ ion
↑↓ ↑ ↑ ↑ ↑ ↑↓
↑↓ ↑↓ ↑
(ii) Fe2+ ion vacant d2sp3 hybrid orbitals
3d 4s 4p
(v) d2sp3 hybrid orbitals in [Fe(CN)6]3–
↑↓ ↑ ↑ ↑ ↑
↑↓ ↑↓ ↑ ××××××××××××
(iii) Fe2+ ion under the influence of strong CN– ligands 6 pairs of electrons from
3d 4s 4p 6 CN– ligands
↑↓ ↑↓ ↑↓
(vi) Octahedral shape of [Fe(CN)6]3– ion is given as:
(iv) d2sp3 hybrid orbitals of Fe2+ ion 3–
CN
↑↓ ↑↓ ↑↓ CN CN
vacant d sp hybrid orbitals
2 3
Fe
(v) d sp hybrid orbitals in [Fe(CN)6]4–
2 3
↑↓ ↑↓ ↑↓ ×××××××××××× CN CN
CN
6 pairs of electrons from
Figure 20.14 Octahedral Shape of [Fe(CN)6]3–Ion
6 CN– ligands
(vii) It has one unpaired electron, that is, n = 1, (iii) d2sp3 hybrid orbitals of Cr3+ ion
μ = √1 (1 + 2) = √3
↑ ↑ ↑
Hence, it is paramagnetic in nature.
vacant d2sp3 hybrid orbitals
• Hexaaqua iron(II) ion [Fe(H2O)6]2+ The formation
of [Fe(H2O)6]2+ complex ion by valence bond method (iv) d2sp3 hybrid orbitals in [Cr(NH3)6]3+
can be shown as follows: ↑ ↑ ↑ ××××××××××××
(i) Fe atom 6 pairs of electrons from
3d 4s 4p 4d 6 NH3 ligands
↑↓ ↑ ↑ ↑ ↑ ↑↓
(v) Octahedral shape of [Cr(NH3)6]3+ ion is given as:
(ii) Fe2+ ion
3d 4s 4p 4d 3+
NH3
↑↓ ↑ ↑ ↑ ↑ NH3 NH3
(iii) sp3d2 hybrid orbitals of Fe2+ ion Cr

3d
↑↓ ↑ ↑ ↑ ↑ NH3 NH3
NH3
vacant sp3d2 hybrid orbitals
Figure 20.16 Structure of [Cr(NH3)6]3+ ion
(iv) sp3d2 hybrid orbitals in [Fe(H2O)6]2+
↑↓ ↑ ↑ ↑ ↑ ×××××××××××× (vi) It has three unpaired electrons that is, n = 3,
6 pairs of electrons from μ = √3 (3 + 2) = √15
6 H2O ligands Hence, it is paramagnetic in nature.
(v) Octahedral shape of [Fe(H2O)6]2+ ion is given as: • Hexaamminecobalt(III) ion [Co(NH3)6]3+ The
formation of [Co(NH3)6]3+ complex ion by valence
2+ bond method can be shown as follows
H2O
H2O H2O
(i) Co atom
Fe 3d 4s 4p
↑↓ ↑↓ ↑ ↑ ↑ ↑↓
H2O H2O
H2O (ii) Co3+ ion
Figure 20.15 Structure of [Fe(H2O)6]2+ Ion 3d 4s 4p
(vi) It has four unpaired electrons, that is, n = 4, ↑↓ ↑ ↑ ↑ ↑
μ = √4 (4 + 2) = √24
(iii) Co3+ ion under the influence of strong NH3
Hence, it is highly paramagnetic (ferromagnetic)
ligands
in nature.
3d 4s 4p
• Hexaamminechromium(III) ion [Cr(NH3)6]3+ The
↑↓ ↑↓ ↑↓
formation of [Cr(NH3)6]3+ complex ion by valence
bond method can be shown as follows: (vi) d2sp3 hybrid orbitals of Co3+ ion
(i) Cr atom
↑↓ ↑↓ ↑↓
3d 4s 4p
↑ ↑ ↑ ↑ ↑ ↑ vacant d2sp3 hybrid orbitals
(v) d2sp3 hybrid orbitals in [Co(NH3)6]3+
(ii) Cr3+ ion
3d 4s 4p ↑↓ ↑↓ ↑↓ ××××××××××××
↑ ↑ ↑ 6 pairs of electrons from
6 NH3 ligands
20.14 Chapter 20
(vi) Octahedral shape of [Co(NH3)6]3+ ion is given as: • TetraammineNickel(II) ion [Ni(NH3)4]2+ The for-
mation of [Ni(NH3)4]2+ complex ion by valence bond
NH3 3+
method can be shown as follows:
NH3 NH3
(i) Ni atom
Co 3d 4s 4p
↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓
NH3 NH3
NH3 (ii) Ni2+ ion
Figure 20.17 Octahedral shape of [Co(NH3)6] ion3+ 3d 4s 4p
↑↓ ↑↓ ↑↓ ↑ ↑
(vii) It has no unpaired electron, that is, n = 0, μ = 0.
(iii) sp3 hybrid orbitals of Ni2+ ion
Hence, it is diamagnetic in nature.
↑↓ ↑↓ ↑↓ ↑ ↑
[Co(CN)6 ]3– and [Co(NO2)6]3– both exhibit similar
vacant sp3 hybrid orbitals
behaviour as [CO(NH3)6]3+
(vi) sp3 hybrid orbitals in [Ni(NH3)4]2+
• Hexafluorocobaltate(III) ion, [CoF6]3– The forma-
tion of [CoF6]3- complex ion by valence bond method ↑↓ ↑↓ ↑↓ ↑ ↑ ××××××××
can be shown as follows: 4 pairs of electrons from
(i) Co atom 4 NH3 ligands
3d 4s 4p 4d (v) Tetrahedral shape of [Ni(NH3)4]2+ ion is given as:
↑↓ ↑↓ ↑ ↑ ↑ ↑↓ NH3 2+
(ii) Co3+ ion

3d 4s 4p 4d Ni
↑↓ ↑↓ ↑ ↑ ↑
NH3 NH3
(iii) sp3d2 hybrid orbitals of Co3+ ion NH3
3d 4s 4p 4d Figure 20.19 Structure of [Ni(NH3)4]2+ complex
↑↓ ↑ ↑ ↑ ↑
(vi) It has two unpaired electrons that is, n = 2,
vacant sp3d2 hybrid orbitals μ = √2 (2 + 2) = √8
(iv) sp3d2 hybrid orbitals in [CoF6]3– Hence, it is paramagnetic in nature.
[Ni(Cl)4]2- behaves similarly as [Ni(NH3)4]2+
↑↓ ↑ ↑ ↑ ↑ ××××××××××××
• Nickel carbonyl [Ni(CO)4] The formation of
6 pairs of electrons from6 F– ligands [Ni(CO)4] complex by valence bond method can be
(v) Octahedral shape of [CoF6]3– ion is given as: shown as follows:
3– (i) Ni atom
F 3d 4s 4p
F F
↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓
Co
(ii) Ni atom after the re-arrangement in the presence
of strong CO ligands
F F
F 3d 4s 4p
Figure 20.18 Structure of [CoF6]3– ion ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
(vi) It has four unpaired electrons, that is, n = 4, (iii) sp3 hybrid orbitals of Ni
μ = √4 (4 + 2) = √24
↑↓ ↑↓ ↑↓ ↑↓ ↑↓
Hence, it is highly paramagnetic (ferromagnetic) in
nature. vacant sp3 hybrid orbitals
(vi) sp3 hybrid orbitals in [Ni(CO)4] (vii) It has no unpaired electron, that is, n = 0, μ = 0.
Hence, it is diamagnetic in nature.
↑↓ ↑↓ ↑↓ ↑↓ ××××××××
4 pairs of electrons from • Tetracyanocuprate(II) ion, [Cu(CN)4]2– The formation
4 CO ligands of [Cu(CN)4]2– complex ion by valence bond method
(v) Tetrahedral shape of [Ni(CO)4] complex is given can be shown as follows:
as: (i) Cu atom
Co 3d 4s 4p
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑
(ii) Cu2+ ion
Ni 3d 4s 4p
↑↓ ↑↓ ↑↓ ↑↓ ↑
Co Co
Co
(iii) Promotion of unpaired 3d electron to a 4 porbital
Figure 20.20 Structure of [Ni(CO)4] complex
3d 4s 4p
(vi) It has no unpaired electron which implies that, n = 0, ↑↓ ↑↓ ↑↓ ↑↓ ↑
μ = 0. Hence, it is diamagnetic in nature.
(iv) dsp2 hybrid orbitals of Cu2+ion
• Tetracyanonickelate(II) ion, [Ni(CN)4] The for- 2–
↑↓ ↑↓ ↑↓ ↑↓ ↑
mation of [Ni(CN)4]2- complex ion by valence bond
method can be shown as follows: vacant dsp hybrid orbitals
2
(i) Ni atom (v) dsp2 hybrid orbitals in [Cu(CN)4]2–

3d 4s 4p ↑↓ ↑↓ ↑↓ ↑↓ ×××××××× ↑
↑↓ ↑↓ ↑↓ ↑ ↑ ↑↓ 4 pairs of electrons from
4 CN– ligands
(ii) Ni2+ ion (vi) Square planar shape of [Cu(CN)4]2– ion is given
3d 4s 4p as:
↑↓ ↑↓ ↑↓ ↑ ↑
2–
(iii) Ni2+ ion under the influence of strong CN– ligands CN CN
3d 4s 4p
↑↓ ↑↓ ↑↓ ↑↓ Cu
(vi) dsp2 hybrid orbitals of Ni2+ion
↑↓ ↑↓ ↑↓ ↑↓ CN CN
vacant dsp2 hybrid orbitals
Figure 20.22 Shape of [Cu(CN)4]2– ion
(v) dsp hybrid orbitals in [Ni(CN)4]2–
2
↑↓ ↑↓ ↑↓ ↑↓ ×××××××× (vii) It has no unpaired electron, that is, n = 0, μ = 0. Hence,

4 pairs of electrons from it is diamagnetic in nature.
4 CN– ligands [Cu(NH3)2]2+ also exhibits similar formation and
(vi) Square planar shape of [Ni(CN)4]2– ion is given nature as shown by [Cu(CN)4]2–.
as:
2– Crystal Field Theory
CN CN Crystal field theory explains the optical properties, the
bonding and other properties of the complexes.
Ni
Features of crystal field theory
CN CN • Ligands are like point charges which show interac-
tion with the central metal atom’s electrons, that is,
they show electrostatic interactions.
Figure 20.21 Square planar shape of [Ni(CN)4]2– ion
20.16 Chapter 20
• As the five d orbitals of an isolated gaseous element 2. When ∆o < P

have the same energy, degeneracy is maintained until Weak field, high spin state [when ∆o small, high spin
the metal atom is surrounded by a symmetric field of state is more stable].
negative charges.
• Due to negative charges, this degeneracy is lost when Magnetic nature and colour of complex
field becomes unsymmetric. Using the principle that a strong field has low spin state
• Due to loss of degeneracy, splitting of d orbitals takes while weak field has high spin state, we can determine
place. It is defined by the nature of the crystal field. whether the electrons are paire. That is, we can find the
magnetic nature and the colour of the complex.
Splitting in octahedral and tetrahedral complexes
Spectrochemical Series
eg
Ligands can be arranged in increasing order of their
eg
strength (ability to cause crystal field splitting) and this
arrangement is referred to as spectrochemical series. It
Energy
∇ ∇
No splitting state 10 q
follows the order:
0
(t2 + eg) orbitals

– – – – – – – – –
(b)
(b) I < Br < S2 < SCN < Cl < F < OH < Ox2 < O2
t2g
t – – –
(t2 + eg) orbitals 2g (c) < H2O < NCS < py < NH3 < en < NO2 < CN < CO.
(a)
Octahedral complex t Applications of crystal field theory

eg • In photography
–
∇
eg AgBr + 2S2O-23
[Ag (S2O3)2]–3 + Br
∇ Excess Soluble complex
Energy
∇ ∇
No splitting state 10 q
• In first group analysis [AgCl, Hg2Cl2, PbCl2]
0
(t2 + eg) orbitals

(b)
(b) AgCl (s) + 2NH3 (aq) [Ag(NH3)2 ]Cl
t2g
t (c)
• In second group, Cd can be precipitated as CdS in
+2
(t2 + eg) orbitals 2g
(a)
presence of Cu+2 with excess of CN-.
Tetrahedral complex t 2Cu2+ + 10 CN – 2[Cu(CN)4]3– + C2N2
Figure 20.23 Crystal Field Energy Splitting Diagram Stable
– – H2S
The difference in the energy of these two sets (eg and t2g) is
∇
Cd2+ + 4CN [Cd(CN)4]2 CdS
called crystal field splitting energy or crystal field stabili-
Unstable
∇
zation energy (CFSE). It is donated by ∆o.
• Ag, Cu, Au are plated from solutions of their cyano
Crystal field stabilization energy depends upon complex ions by electroplating (electroplating bath).
• Oxidation state of central metal atom At anode
∆o ∝ Charge on central metal atom Cu + 4CN – [Cu (CN)4]–3 + e–
• Geometry of complex At cathode
– –
∆o > ∆t [Cu(CN)4]3 + e– Cu + 4CN
• Nature of ligand • Purification of H2O by using EDTA to remove impu-
∆o is low for weak ligands rities of Ca+2, Mg+2.
∆o is high for strong ligands • EDTA is used in the treatment of metal poisoning
(for emample, lead poisoning
Significance of ∆o
• Extraction of Ag, Au is done by the formation of
To define high or low spin state cyanide complexes.
If ∆o is CFSE and if P is the energy needed for electron • Purification of Ni is done by Mond’s method.
pairing in single orbital, then
Ni + 4CO Ni [CO]4
1. When ∆o > P ∆
Strong field, low spin state [∆o is large, low spin state is [Ni(CO)4] Ni + 4CO
more stable].
• In the test of Ni2+ using DMG (Dimethyl glyoxi- Preparation

mate), blood red blood coloured chelate is formed. • By direct reaction of metals
• Cis-platin, that is, cis-diamminedichloro platinum R-X + Mg
(C2H5)2O
R–Mg–X
(II) [Pt (NH3)2 Cl2], is used in the treatment of can-
Grignard reagent
cer. It can damage the kidney so these days dinuclear (C2H5)2O
Pt-complex is used instead. R-X + 2M R–M + M X
(C2H5)2O
• Animal and plant world Chlorophyll is a complex of n-C4H9Br + 2Li n-C4H9–Li + LiBr
Mg2+ and haemoglobin is a complex of Fe2+. n-butyllithium
• Vitamin B12 is a complex of Co2+. 2C2H5Br + 2Zn (C2H5)2Zn + ZnBr2
• Aryl arsenic compounds are used as chemotherapeu- Diethyl zinc
tic agents. • By use of alkylating reagents
Ether
• (C2H5) HgCl is used as a fungicide for the protection PCl3 + 3C6H5MgCl P(C6H5)3 + 3MgCl2
of young plants. Triphenyl phosphine
• Heterogeneous catalysis Zeigler–Natta catalyst, CdCl2 + 2C2H5MgCl
Ether
(C2H5)2Cd + 2MgCl2
TiCl4 + (C2H5)3Al is used for the polymerization of Diethyl cadmium
olefins. Ether
SnCl4 + 4n-C4H9Li (n-C4H9)4Sn + 4LiCl
• Homogeneous catalysis Hydrogenation of alkenes Ether
PbCl4 + 4C2H5MgBr (C2H5)4 Pb
by using the Wilkinson’s catalyst, (Ph3P)3RhCl.
Tetraethyl lead
• Electroplating of metals involves the use of complex
salts as electrolytes. For example, use of K[Ag(CN)2] π-bonded organometallic compounds
in silver plating. These are formed mainly by transition elements. Here, a
normal σ-bond is formed through the π-cloud of electrons
of the organic molecule. For example, Ferrocene, [Fe
ORGANOMETALLIC COMPOUNDS (η5–C5H5)2 ]
• The compounds in which a metal atom, a metalloid H H
(Ge, As, Sb, Te) or a non-metal atom like B, Si, P C
(less electronegative than C) is directly linked with C
the carbon atom of a hydrocarbon molecule or a rad- H H +
K
ical are called organometallic compounds. For exam-
CI CI
ple, (C2H5)2Zn, and CH3B(OCH3)2 are organometal- (a)
lic compounds. Pt
CI CI
FA C T S TO R E M E M B E R Zeise’s salt
K [PtCI3(η2–C H )]
2 4
B(OCH3)3, metal carbides and metal cyanides are not
organometallic, though M–C bond exists in them.
Types of Organometallic Compounds
σ-bonded organometallic compounds

• These are formed from non-metallic and metal- (b) Fe (c)
Cr
loid elements (except Zn, Cd, Hg) by a normal two
electron covalent bond. For example, R–Mg–X,
(C2H5)2Zn, (CH3)4Si, (C2H5)4 Pb, B(CH3)3, (CH3)3Al,
LiCH3.
• Trimethyl aluminium exists as a stable dimer where
Ferroncne Dibenzene chromium
two methyl groups act as bridge between two Al
Fe(η5 –C5H5)2 Cr(η6 –C6H )2
atoms. 6
Figure 20.24 Examples of π-bonded organometallic
compounds
20.18 Chapter 20
Zeisse’s salt, K[PtCl3 (η2–C2H4)] Structure and bonding in metal carbonyl

Dibenzene chromium, [Cr (η6–C6H6)2] Homoleptic binary metal carbonyls have simple, well
• Here ηx shows the number of carbon atoms bonded defined structures. The metal atom in them is in zero oxi-
to the metal atom. dation state.
(a) Fe(CO)5 has a trigonal bipyramidal structure
• Ferrocene has a sandwich structure.
CO
• Pentamethyl cyclopentadienyl ligand C5Me5 forms CO
stable f-block compounds. For example, [Th H (OR) OC Fe
(C5Me5)2] CO
CO
Preparation
Figure 20.26 Structure of Pentacarbonyl iron(0)
(a) Preparation of zeise’s salt
H2C = CH2 + K2PtCl4 [PtCl3(C2H4)- K+] + HCl (b) M(CO)6 is octahedral,where M = Cr, V, Mo or W.
Zeise’s salt
OC CO
OC
(b) Preparation of ferrocene CO
CO
2C2H5MgBr + FeCl2 [(C5H5)2Fe] + 2MgBrCl Cr
Ferrocene CO
OC CO
(c) Preparation of dibenzene chromium
Figure 20.27 Structure of Hexacarbonyl chromium(0)
2 C6H6 + Cr [(C6H6)2 Cr]
Dibenzene chromium (c) [Mn2(CO)10] is made up of two square pyramidal
Mn(CO)5 units joined by a Mn–Mn bond
σ- and π-bonded organometallic compounds (d) [Co2(CO)8] has a Co–Co bond bridged by two CO
• Transition metal carbonyls belong to this class of groups.
organometallics. For example, Homoleptic car-
bonyl M(CO)x (compounds containing carbonyl Applications of Organometallic
ligands only) Here M = V, Cr, Mo, W.; [Ni(CO)4], Compounds
[Fe(CO)5].
CO As homogeneous catalysts
Ni Selective hydrogenation of certain double bonds using
CO Wilkinson’s catalyst, (Ph3P)3RhCl.
OC CO (Et3P)2NiCl2 acts as catalyst for the isomerization of
Figure 20.25 Structure of Tetracarbonyl nickel(0) alkenes.
• Polynuclear carbonyls–[Co2(CO)8], [Fe2 (CO)9]
• In a metal carbonyl, the metal–carbon bond possesses As heterogenous catalysts
both σ- and π-character. A σ-bond between metal and Zeigler–Natta catalyst (a solution of TiCl4, containing
carbon atom is formed, when a vacant hybrid bond triethylaluminium) for the polymerization of ethylene and
of the metal atom overlaps with an orbital on C the other alkenes.
atom of carbon monoxide containing a lone pair of • Organometallic compounds of magnesium (R–Mg –X),
electrons. cadmium (R2Cd) and lithium (R–Li) are extensively
• Formation of a π-bond takes place when a filled used in organic synthesis.
orbital of the metal atom overlaps with a vacant • Tetraethyl lead is used as an anti-knocking com-
anti-bonding π* orbital of C atom of carbon mon- pound in petrol.
oxide. This overlap is also called back donation of • A number of organometallics also find application
electrons by metal atom to carbon. in agriculture. For example, ethyl mercury chloride,
• The π-overlap is perpendicular to the nodal plane of C2H5HgCl, is used as a fungicide for the protection
σ-bond. of young plants and seeds against fungal infection.
• In olefinic complexes, the bonding π-orbital electrons • Aryl arsenic compounds are used as chemotherapeu-
are donated to the empty orbital of the metal atom tic agents.
and at the same time to the back bonding π-orbital of
the olefin. In analytical chemistry
Preparation
Ni + 4CO Ni(CO)4 Coordinate compounds are effectively used in both qualita-
Fe + 5CO Fe(CO)5 tive and quantitative analysis. For example,
• In first group analysis [AgCl, Hg2Cl2, PbCl2] • The red colour of haemoglobin is due to the presence
AgCl (s) + 2NH3 (aq) [Ag(NH3)2 ]Cl of non-proteinaceous part called heme.
• Haemoglobin contain one porphyrin ring and one
• In second group Cd can be precipitated as CdS in
+2
iron atom. In human beings the haemoglobin iron is
presence of Cu+2 with excess of CN–.
– nearly 0.34 per cent.
2Cu2+ + 10 CN 2[Cu(CN)4]3– + C2N2 • Its molecular weight is 16,400, however, the molec-
Stable ular weight obtained by ultra centrifugation is nearly
65,000, which means that four units of heme form an
–
Cd2+ + 4CN [Cd(CN)4]2– aggregate molecule in haemoglobin.
Unstable • If ferroporphyrin has Fe in the form of Fe2+ it is
H2S called protoheme and if metalloporphyrin has Fe3+
CdS
it is called haematins.
In extraction of metals • Histidine (amino acid) is present in globin or protein
part of haemoglobin.
Extraction of Ag, Au is done by the formation of their cya- • The primary function of blood is transportation.
nide complexes as follows: Haemoglobin carries oxygen from lungs to tissues.
Ag2S + 4NaCN 2Na[Ag(CN)2] + Na2S • It is circulated throughout the body by the pumping
4Na2S + 5O2+ 2H2O 2Na 2SO4+ 4NaOH + 2S action of heart.
• The binding of O2 molecule with haemoglobin is
2Na[Ag(CN)2] + Zn Na2[Zn(CN)4] + 2Ag
oxygenation and such haemoglobin is called oxy-
4Ag + 8NaCN + O2 + 2H2O 4Na[Ag(CN)2] haemoglobin (HbO2).
+ 4NaOH • It is the vehicle for metabolic communication
• Purification of Ni is done by Mond’s method. between the organs of the body.
Ni + 4CO Ni [CO]4 • Haemoglobin transports nutrients from small intes-
[Ni(CO)4] ∆ Ni + 4CO tine to the liver and other organs and also transports
waste products to the kidneys for excretion.
• Electroplating of metals involves the use of complex
• It is also a mean for the transportation of oxygen
salts as electrolytes K[Ag(CN)2] is extensively used
from the lungs to the tissues and for transport of CO2
in silver plating.
generated during the respiratory metabolism of the
Biological applications tissues to lungs for excretion.
• Affinity of haemoglobin for oxygen decreases due to
• Cis platin that is, cis-diamminedichloro platinum(II) decrease in pH, therefore, the blood is well buffered
[Pt (NH3)2 Cl2] is used in the treatment of cancer. It by carbonates which thereby maintain a pH value
was found that its use led to kindly damage, there- between 7.36–7.42.
fore, dinuclear Pt-complex is now used in its place.
• Chlorophyll is a complex of Mg2+ and haemoglobin Chlorophyll
is a complex of Fe2+. • Chlorophyll is the green pigment present in the
• Vitamin B12 is a complex of Co .2+ leaves of plants.
• Aryl arsenic compounds are used as chemotherapeu- • It is a magnesium complex which is of two types:
tic agents. Chlorophyll ‘a’ and chlorophyll ‘b’.
• The covalency of Mg2+ in chlorophyll is four and it
• (C2H5) HgCl is used as a fungicide for the protection
is satisfied by nitrogen atoms present in the pyrrole
of young plants.
rings of tetrapyrrole.
• Chlorophyll has a tetrapyrrole ring structure in which
Coordination Compounds in Biological Mg2+ is present in the centre.
System
• Chlorophyll ‘a’ has a methyl group on β-carbon of
Haemoglobin one of the pyrrol ring but when in place of a methyl
• Haemoglobin is a red coloured conjugated globu- group a formyl group is substituted it is then called
lar protein present in blood having four polypeptide chlorophyll ‘b’.
chains (tetrahedral).
20.20 Chapter 20
• Chlorophyll ‘a’ can absorb violet blue (4300 Å) and • Vitamin B12 does not occur in plants however it is
red light (6800 Å). during photosynthesis, this red present in rain water.
light is used by the plants. • Human blood has nearly 2 × 10–4 g of vitamin B12 per
• In photosynthesis; CO2 and water vapour from air litre.
undergo chemical combination in light in presence of • It promotes the formation of normal erythrocytes
chlorophyll to produce glucose and oxygen thereby (RBC).
making chlorophyll responsible for the production of • Vitamin B12 has a nucleotide like structure and a
carbohydrates in plants. corrin ring system. The corrin ring looks like
porphyrin, however, the two rings are directly joined
sun light
6CO2 + 6H2O C6H12O6 + 6O2 instead of joining by–CH = linkage was found in
chlorophyll porphyrin.
• chlorophyll also helps to maintain O2 and CO2 equi- • Here, Co3+ ion is hexacoordinated by the four nitrogen
librium in nature. atoms of corrin ring so vitamin B12 is called cobalamin.
Due to the presence of one cyanide group vitamin
• Biomolecules are the organic compounds present
B12 is also called cyanocobalamine.
as essential constituents in different cells of living
Co3+ is required to maintain normal bone marrow
organisms.
function for the production of RBC. its deficiency
leads to nutritional type of anemia while its excess
Vitamin B12 or cyanocobalamin (C63H88CoN14O14P) causes polyerythrymia.
• The main sources of vitamin B12 are food products
like meat, fish, egg, milk.
• It contains carbon, hydrogen, osygen, nitrogen, phos-
phareus and cobalt. It’s deficiency causes pernicious
anemia.
CONCEPTS AT A GLANCE
 Optical Isomerism in Chelated Tetrahedral and Square donor atoms of the similar ligands occupy adjacent positions
Planar Complexes In tetrahedral complexes, optical isom- at the corners of the same face of an octahedron.
erism is observed only in case of bichelates having unsym-
NH33
NH
metrical ligands. This has been observed in Be(II), B(III),
Zn(II), Co(II) complexes which are generally represented H3N Br
as
Co
A B B A
H3N Br
Br
M M
A B B A Br
For example, Figure 20.30 Structure of Facial or Fac-Isomer

1. bis(salicylaldehyde)boron(III) cation has been found to be  The other geometric isomer of the compound is called
racemic and resolution has been accomplished. meridional (mer) if the positions occupied are around the
meridian of the octahedron.
O + O +
CH HC NH33
NH
H33N
H N Br
C6H4 H4C6
B B Co
O O O O Br Br
HC CH NH3
H4C6 O C6H4
O Figure 20.31 Representation of Meridional or
Figure 20.28 Bis(salicylaldehydo)boron(III) d-and l-forms of Mer Isomer
[B(C6H4O.CHO)2]+ ion
 Irving William order In case of M2+, 3d-series, the stabil-
ity of complexes increases as follows:
2. The two enatiomers of bis(benzoylacetonato) beryllium(II) Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ < Zn2+
are shown as follows:
CH3 CH3 H3C H3C

C O O C C O O C
HC Be CH HC Be CH
C O O C C O O C
C6H5 C6H5 H5C6 H5C6
Figure 20.29 Bis(benzoylacetonato)beryllium(II) d-and l- forms of

[Be(C6H5CO.CH.CO.CH3)2] Complex.
 K3[Co(NO2)6] that is potassium hexanitrocobaltate (III) is

called Fischer’s salt. Its common chemical name is potas-
sium cobaltinitrite.
 The geometric isomer is called facial (fac) when each trio of
20.22 Chapter 20
EXERCISES
Single Option Correct Type
1. Which of the following is a complex salt? 10. Pentaamminenitrocobalt (III) cation possesses the
(a) KCl.MgCl2.6H2O property of
(b) FeSO4.(NH4)2 SO4.6H2O (a) physiosorption
(c) 4KCN.Fe(CN) (b) chirality
(d) K2SO4.Al2(SO4)3.24 H2O (c) linkage isomerism
2. The number of ions formed on dissolving one mole- (d) versatile reducing agent
cule of FeSO4 (NH4)2 SO4.6H2O are 11. The anion [Co(C2O4)3]3– involves which type of
(a) 3 (b) 4 hybridization?
(c) 5 (d) 6 (a) d2sp3 (b) sp3d2
3. What is the coordination number of metal in [Co(en)2 (c) d sp
3 2
(d) sp2d3
Cl2]? 12. The correct IUPAC name of KAl(SO4)2 .12H2O is
(a) 3 (b) 4 (a) aluminium potassium sulphate-12-water
(c) 5 (d) 6 (b) potassium aluminium(III) sulphate-12-water
4. EDTA is a ……. ligand. (c) potassium aluminium(III) sulphate hydrate
(a) tetradentate (b) hexadentate (d) aluminium(III) potassium sulphate hydrate-12
(c) bidentate (d) tridentate 13. Atomic numbers of Cr and Fe are respectively 25 and
5. Diethylenetriamine is a 26. Which of the following is paramagnetic due to the
(a) chelating agent spin of the electron?
(b) polydentate ligand (a) [Cr(NH3)6]3+ (b) [Fe(CO)5]
(c) tridentate ligand (c) [Cr(CO)6] (d) [Fe(CN)6]4–
(d) all of these 14. The hypothetical complex chlorodiaquatriammineco-balt
6. In the spectrochemical series, the magnitude of the (III) chloride can be presented as
crystal field splitting is maximum for which ion? (a) [Co (NH3)3 (H2O)3] Cl3
(a) F – (b)NO2– (b) [Co (NH3)3 (H2O)2 Cl]
(c) CN –
(d) Cl– (c) [Co (NH3)3 (H2O) Cl3]
7. The correct name of the compound [Cu(NH3)4](NO3)2 (d) [CoCl (NH3)3 (H2O)2] Cl2
according to system is 15. Which disease is cured by using Gold (I) thiomaleate
(a) tetraamminecopper(II) dinitrite as a medicine?
(b) tetraamminecopper(II) nitrite (a) diabetes (b) ulcer
(c) cuprammonium nitrate (c) arthritis (d) malaria
(d) tetramminecopper(II) nitrate
16. Considering H2O as a weak field ligand, the number of
8. Which of the following complex species does not unpaired electrons in [Mn(H2O)6]2+ will be (Atomic
involve inner orbital hybridization? no of Mn = 25)
(a) [Co(NH3)6]3+ (b) [Cr(NH3)6]3+ (a) 2 (b) 3
(c) [CoF6] 3–
(d) [Fe(CN)6]3 (c) 4 (d) 5
9. The complex [Co(NH3)5Br]SO4 will give a white pre- 17. The complex used as an anti-cancer agent is
cipitate with (a) mer-[Co(NH3)3Cl3] (b) cis-[PtCl2 (NH3)2]
(a) PbCl2 (b) AgNO3 (c) cis-K2[PtCl2Br2] (d) Na2CoCl4
(c) KI (d) none
18. Which of the following is not considered as an ogano- 27. The water soluble complex among the following is
metallic compound? (a) [Ni(HDMG)2 Cl2]
(a) ferrocene (b) cisplatin (b) [Ni(CO)4]
(c) Grignard's reagent (d) zeise’s salt (c) [Ni(HDMG)2]
(d) [Pd (NH3)2Cl2]
19. Which of the following does not have an optical
isomer? 28. The correct IUPAC name of AlCl3(EtOH)4 is
(a) [Co(en)2 Cl3] (b) [Co(en)2Cl2]Cl (a) Aluminium (II) chloride-4-ethanol
(c) [Co(NH3)3Cl3] (d) [Co(en)(NH3)2Cl2]Cl (b) Aluminium(III) chloride-4-ethanol
(c) Aluminium(IV) chloride-4-hydroxy ethane
20. The correct name of the given compound is
(d) Aluminium chloride-4-ethanol
Co
29. Which is not a pi-acceptor ligands among the follow-
(Co)3 Fe Co Fe (Co)3
ing ligands (CH3)3P, NO+, CN– and I3–?
Co
(a) CN– (b) I3–
(a) μ-tricarbonyl bistricarbonyl iron(0) (c) (CH3)3P (d) NO+
(b) hexacarbonyl iron (III)μ-tricarbonyl ferrate(0) 30. The formula of a carbonyl complex of cobalt (CO)n
(c) tricarbonyl iron (0)μ-tricarbonyl iron (0) Co–Co(CO)n in which there is single covalent CO–
(d) all of these CO bond is
21. The species having tetrahedral shape is (a) Co2(CO)8 (b) Co2(CO)10
(a) [PdCl4]2 – (b) [Ni(CN)4]2– (c) Co(CO)4 (d) Co(CO)8
(c) [Pd(CN)4] 2–
(d) [NiCl4]2– 31. The effective atomic number (EAN) of Cr in
24
22. Among the following complex ions, the species con- [Cr(NH3)6]Cl3 is
taining Fe3+ in strong ligand field is (a) 24 (b) 27
(a) [FeF6]3– (b) [Fe(NH3)6]3+ (c) 30 (d) 33
(c) [Fe(CN)6] 3–
(d) [Fe(H2O)6]3+ 32. The IUPAC name for [Be4O(CH3COO)6] is
23. Which one of the following is a correct representation (a) Basic beryllium acetate(II)
of tetraamminecopper(II) hexacyanoferrate(II)? (b) hexa-μ-hexakis (acetato) beryllium(II)
(a) [Cu(NH3)4]3 [Fe(CN)6]2 (c) hexa-μ-acetato(O, O’)-μ4-oxotetraberyllium(II)
(b) [Cu(NH3)4] [Fe(CN)6]2 (d) hexaacetato-μ-oxoberyllium(II)
(c) [Cu(NH3)4] [Fe(CN)6] 33. The structure of iron pentacarbonyl is
(d) [Cu(NH3)4]3 [Fe(CN)6]
(a) square planar (b) trigonal bipyramid
24. The complex compound used in the chemotherapy of (c) triangular (d) none
cancer is
34. The two complex given below are
(a) cis-[PtIV (NH3)2 Cl4]
(b) trans-[PtII (NH3)2 Cl2] A
A A en
(c) cis-[PtIV (NH3)4 Cl2] Cl2
en M en M
(d) cis-[PtII (NH3)2 Cl2]
A
25. An example of hexadentate ligand is A en
en
(a) iminodiacetate ion
(b) 2, 2’bipyridyl (a) geometrical isomers
(c) dimethyl glyoxime (b) position isomers
(d) ethylene diamine tetraacetate ion (c) optical isomers
(d) identical
26. Haemoglobin, a complex containing iron is a
const-ituent of blood. The oxidation state of iron in 35. The oxidation state of oxygen in O2[PtF6] is
the complex is (a) – ½ (b) +2
(a) +1 (b) +2 (c) + ½ (d) +1
(c) +3 (d) +4 36. A 0.01 M complex of CoCl2 and NH3 (molar ratio
20.24 Chapter 20
1:4) is found to have effective molarity of 0.02 M of Cr = 24] is

(evaluated from colligative property). What is the for- (a) 2 (b) 3
mula of the complex? (c) 4 (d) 5
(a) [Co (NH3)4 Cl2] Cl
44. [FeII(O2)(CN)4Cl]4– is named as
(b) [Co (NH3)3 Cl3]
(c) [Co (NH3)4] Cl3 (a) chlorotetracyanodioxoferrate(II) ion
(d) [Co (NH3)5 Cl] Cl (b) chlorotetracyanoperoxoferrate(II) ion
(c) chlorotetracyanosuperoxoferrate(II) ion
37. The correct IUPAC name of Mn3(CO)12 is
(d) chlorotetracyanooxoferrate(II) ion
(a) manganic dodecacarbonyl (0)
(b) dodecacarbonyl trimanganese (0) 45. Which one has the highest paramagnetism among the
(c) dodecacarbonyl manganic (II) following ions?
(d) dodecacarbonyl manganate (0) (a) [Cr(H2O)6]3+
(b) [Fe(H2O)6]2+
38. If NH4OH is added to the (PtCl4)2– ion, the complex
(c) [Cu(H2O)6]2+
formed represents
(d) [Zn(H2O)6]2+
(a) zero dipole (b) infinite dipole
(c) finite dipole (d) all of these 46. The compound which does not show paramagnetism is
(a) [Cu(NH3)4]Cl2
39. The geometry of Ni(CO)4 and Ni(PPh3)2Cl2 are
(b) [Ag(NH3)2]Cl
(a) both square planar (c) NO
(b) tetrahedral and square planar (d) NO2
(c) both tetrahedral
(d) square planar and tetrahedral 47. According to IUPAC nomenclature sodium nitro-
40. The phenomenon of optical activity will be shown by prusside is named as
(a) sodium pentacyanonitrosyl ferrate (II)
(b) sodium pentacyanonitrosyl ferrate (III)
(c) sodium nitroferriccyanide
(d) sodium nitroferrocyanide
(a) (b) 48. The correct name for the coordination compound,
[Cr(en)3] [Co(C2O4)3] is
(a) tris-(ethylenediamine)chromate(III) trioxalato-cobalt(III)
(b) tris-(ethylenediamine) chromium(III)trioxalato-
co-baltate (III)
(c) tris-(ethylenediamine)chromate(III)trioxalatoco-
baltate(III)
(c) (d) None of these
(d) tris-(ethylenediamine)chromaium(III)trioxalato-
cobalt(III)
49. The complex ion [Co (en)2 Cl2]+ exhibits
41. The IUPAC name for K2[OsCl5N] is (a) optical isomerism and linkage isomerism
(a) potassium pentachloroazidoosmate(VIII) (b) cis-trans isomerism and optical isomerism
(b) potassium pentachloroazidoosmate(VI) (c) cis-trans isomerism and linkage isomerism
(c) potassium pentachloronitridoosmate(VI) (d) cis-trans isomerism only
(d) potassium nitroosmate(III)
50. Which of the following species has a square planar
42. Which of the following is an organometallic compound? structure?
(a) lithium methoxide (b) lithium acetate (a) [SF6] (b) [Pt(NH3)2Cl2]
(c) lithium dimethylamide (d) methyl lithium (c) [BeF4]2– (d) [Hg(NH3)2]Cl2
43. The number of d electrons in [Cr(H2O)6]3+ [atomic no. 51. Oxidation number of Cr in the following complex is
3+ 58. [(C6H5)2 Pb (SCN)2] and [(C6H5)2 Pb (NCS)2] are

O22
O
(a) linkage isomers
(H2O)6 Cr Cr(H2O)6
O O
O (b) coordination isomers
(c) ionization isomers
(a) 3 (b) 6 (d) geometrical isomer
(c) 4 (d) 5 59. Formula of ferrocene is
52. In the complex ion, [Cr(C2O4)2 (H2O)2] , the oxida- –
(a) [Fe(CN)6]4– (b) [Fe(CN)6]3+
tion number of Cr is (c) [Fe(CO)5] (d) [(C6H5)2Fe]
(a) +1 (b) +2 60. The oxidation state of Mo in its oxo-complex species
(c) +3 (d) +4 [Mo2O4 (C2H4)2 (H2O)2]2– is
53. The correct IUPAC name for the complex ion [CoCl (a) + 2 (b) + 3
(ONO) (en)2]+ is (c) + 4 (d) + 5
(a) bis(ethylenediamine)chloronitrito-O-cobalt 61. In photography, hypo is used in the reduction of
(III) ion
(a) Ag from AgBr
(b) bis(ethylenediamine)chloronitrito-O-cobaltate
(b) AgBr into Ag2SO4
(III) ion
(c) AgBr into soluble thiosulphate complex
(c) chlorodiethyldiamine nitrite-O-cobalt(III) ion
(d) both (b) and (c)
(d) chlorodiethyl diamine nitrocobalt(III) ion
62. In the silver plating of copper, K[Ag(CN)2] is used
54. The IUPAC name for [Ru(NH3)2 (en)(NO3)2] is
instead of AgNO3. The reason is
(a) diammine(ethylenediamine) nitratoruthenium(III)
(a) less availability of Ag+ ions, as Cu cannot displace
(b) diammine(ethylenediamine)ruthenium (II) nitrate
Ag from [Ag(CN)2]– ion
(c) diamminebis(ethylenediamine) ruthenium(III)
(b) more voltage is required
nitrate
(c) a thin layer of Ag is formed on Cu
(d) (ethylenediamine) diamineruthenium(II)nitrate
(d) Ag+ ions are completely removed from solution
55. Which one of the following is true?
63. Among the following complex ions, the one with the
(a) The charge on the complex ion in K2[PtCl4] is +2 highest paramagnetism is
(b) The coordination number of Hg in [Hg(en)2]2+ is
(a) [FeF6]2+ (b) [Cu(H2O)6]2+
4 (here en is ethylenediamine)
(c) [Zn(H2O)6] 2+
(d) [Cr(NH3)6]3+
(c) The oxidation number of iron in [Fe(CN)6]4– is +6.
64. The ligand shown here is
(d) In transition metal complexes, ligands act as
lewis acid
56. The compounds shown in the diagram are N N
N N
H3C H3C (a) Tridendate (b) 1, 10-phenanthroline

(c) 1, 10-phenanthrine (d) 2, 2-dipyridyl
O O
M and M 65. What does the complex, tris-(ethylenediamine)cobalt
O O (III) chloride exhibit?
(a) cis-trans isomerism (b) fac-mer isomerism
H3C H3 C (c) linkage isomerism (d) optical isomerism
66. The EAN of platinum in potassium hexachloroplati-
(a) linkage isomers (b) resonating forms
nate (IV) is
(c) positional isomers (d) coordination isomers
(a) 46 (b) 86
57. Optical isomerism is not shown by the complex (c) 36 (d) 84
(a) [Co(en)2 Cl2]+ (cis-form)
(b) [Cr(en3)]3+ 67. Which of the following are diamagnetic?
(c) [Co(en)2 Cl2]+ (trans-form) (1) K4[Fe(CN)6] (2) K3[Cr(CN)6]
(d) [Cr(ox)3]3– (3) K3[Co(CN)6] (4) K2[Ni(CN)4]
20.26 Chapter 20
Select the correct answer using the codes given below: 75. Which one of the following does not obey EAN rule?
(a) 1 and 2 (b) 2, 3 and 4 (a) V(CO)6 (b) Mn2(CO)10
(c) 1, 3 and 4 (d) 2 and 4 (c) Fe(CO)5 (d) K4Fe(CN)6
68. Which one of the following can show optical 76. The complex ion which has no d electrons in the
isomerism? central metal atom is (Atomic number Cr = 24,
Mn = 25, Fe = 26, Co = 27)
(a) K3[Fe(CN)6] (b) Cr[(NH3)6]Cl3 – +
(a) [MnO4] (b) [Co(NH3)6]3
(c) FeSO4.7H2O (d) K3[Cr(C2O4)3] (c) [Fe(CN)6]3
–
(d) [Cr(H2O)6]3
+
69. Which of the following will give four isomers? 77. Which of the following statement is incorrect?
(a) [Co(en)2 Cl2] Br (a) in K3[Fe(CN)6], the ligand has satisfied both
(b) [Co (en) (NH3)2 Cl2] Cl primary and secondary valencies of ferric ion
(c) [Co (PPh3)2 (NH3)2 Cl2] Cl (b) in K3[Fe(CN)6] the ligand has satisfied only the
(d) [Co (en)3] Cl3 secondary valency of ferric ion
(c) in K4[Fe(CN)6] the ligand has satisfied both
70. Which one of the following high spin complexes has the primary and secondary valencies of ferrous ion
largest CFSE (Crystal Field Stabilization Energy)? (d) in [Cu(NH3)4]SO4, the ligand has satisfied only
+ +
(a) [Cr(H2O)6]2 (b) [Cr(H2O)6]3 the secondary valency of copper
2+ +
(c) [Mn(H2O)6] (d) [Mn(H2O)6]3
71. Which one is the most likely structure of CrCl3.6H2O 78. The number of chloride ions produced by the com-
is 1/3 of total chlorine of the compound is precipitated plex tetraamminechloroplatinum(IV) chloride in an
by adding AgNO3 to its aqueous solution? aqueous solution is
(a) [Cr(H2O)3Cl3].(H2O)3 (a) 1 (b) 2
(c) 3 (d) 4
(b) CrCl3. 6H2O
+ + + +
(c) [CrCl (H2O)5]Cl2 .H2O 79. While Ti3 , V3 , Fe3 and Co2 can afford a large num-
+
(d) [CrCl2 (H2O)4].Cl. 2H2O ber of tetrahedral complexes, Cr3 never does this, the
72. Tetrahedral complexes of the types of [Ma4] and reason being
[Ma3b] (here M = Metal, a, b = Achiral ligands) are (a) crystal field stabilisation energy in octahedral
not able to show optical isomerism because vis-à-vis tetrahedral Cr3+ system plays the decid-
(a) these molecules/ions have non super imposable ing role
+
mirror images (b) Cr3 forces high crystal field splitting with a
(b) these molecules possess a centre of symmetry varieties of ligands
(c) these molecules/ions possess a plane of symme- (c) electronegativity of Cr3+ is the largest among these
try and hence are achiral trivalent 3d-metals and so chromium prefers to be
(d) these molecules/ions possess Cn axis of symmetry associated with as many ligands as its radius
permits
73. The complex salt having the molecular composition
[Co(NO2)(SCN)(en)2]Br exhibits (d) both (b) and (c)
(a) linkage isomerism only 80. The blue colour obtained in the Lassaigne's test is due
(b) ionization isomerism only to formation of the compound
(c) cis-trans isomerism only (a) Fe4[Fe(CN)6]3 (b) Fe4[Fe(CN)6]
(d) all of these
(c) Na4[Fe(CN)6] (d) Fe3[Fe(CN)6]4
74. Isomerism shown by octahedral complex [Co(NH3)4
Br2]Cl are 81. Which one of the following octahedral complexes
(a) geometrical and ionization will not show geometric isomerism? (A and B are
(b) optical and ionization monodentate ligands)
(c) geometrical and optical (a) [MA4B2] (b) [MA5B]
(c) [MA2B4] (d) [MA3B3]
(d) only geometrical
82. The formula of tetrachlorodiammineplatinum(IV), is 90. For a complex MA3B3 possessing a trigonal prismatic
(a) [Pt(NH3)2] Cl4 (b) [Pt(NH3)2 Cl4] geometry, the number of possible isomers are
(c) [Pt(NH3)2 Cl2]Cl2 (d) K4[Pt(NH3)2 Cl4] (a) 3 (b) 4
(c) 5 (d) 6
83. The possible numbers of isomers for the complex
[MCl2 Br2] SO4 will be 91. The coordination number and oxidation number of M
(a) 5 (b) 4 in the compound [M(SO4)(NH3)5] will be
(c) 3 (d) 2 (a) 6 and 3 (b) 2 and 6
84. Predict which is the strongest ligand from the stability (c) 6 and 2 (d) 3 and 6
constant (hypothetical values) given below?
92. The complex with spin-only magnetic moment of
[Cu (H2O)4]2 , K = 9.5 × 108
+ +
(a) Cu2 + 4H2O ~ 4.9 B.M. is
[Cu (en)2]2 ,
+ +
(b) Cu2 + 2en K = 3.0 × 1015 (a) [Fe(CN)6]3
+
[Cu(CN) ]2 ,
+ –
(c) Cu2 + 4CN 4
K = 2.0 × 1027 (b) [Fe(H2O)6]3
+
+ +
(d) Cu2 + 4NH3 [Cu(NH3)4]2 , K = 4.5 × 1011 (c) [Fe(CN)6]4
–
85. In which of the following pairs, the EAN of the cen- +

(d) [Fe(H2O)6]2
tral metal atom is not the same?
+
(a) [FeF6]3 and [Fe(CN)6]3
– 93. The number of isomers possible for complex K2[Pd
–
(b) [Fe(CN6)]3 and [Fe(CN)6]4
– Cl Br (SCN)2] is
+
(c) [Cr(NH3)6]3 and [Cr(CN)6]3
– (a) 1 (b) 2
– (c) 3 (d) 4
(d) [Ni(CO)4] and [Ni(CN)4]2
86. Name the metal M which is extracted on the basis of 94. Which of the following will have three stereo-isomeric
following reactions: forms?
– (1) [Cr (NO3)3 (NH3)3]
4M + 8CN + 2H2O + O2 4[M(CN)2]– 1 + 4OH–
–
(2) K3 [Co(C2O4)3]
2[M (CN)2]–1 + Zn [Zn (CN)4]2 + 2M (3) K3 [Co(C2O4)2Cl2]
(a) Ag (b) Cu (4) [Co(en2)ClBr]
(c) Hg (d) Ni (Here, en = ethylene diamine)
87. Which of the following complex ions will not show (a) 1 and 2 (b) 1 and 3
optical activity? (c) 1 and 4 (d) 3 and 4
+
(a) [Co (en) (NH3)2 Cl2] 95. The value of magnetic moment for a complex ion is
(b) [Cr (NH3)4 Cl2]+ 1.73 BM. The complex ion is
(c) [Pt (Br) (Cl) (I) (NO2) (Py) NH3] (a) [Mn(CN)6]4
–
(d) cis-[Co (en)2 Cl2]+ (b) [Co(NH3)6]2

+
–
88. The number of ions produced from one molecule of (c) [MnF6] 3
–
[Pt (NH3)5 Br] Br3 in the aqueous solution will be (d) [Fe(CN)5 NO]2
(a) 4 (b) 5 96. The number of unpaired electrons in the complex ion
–
(c) 6 (d) 7 [CoF6]3 is (Atomic number of Co = 27)
(a) 4 (b) zero
89. The stability constants of the complexes formed by a (c) 2 (d) 3
+ –
metal ions (M2 ) with NH3, CN , H2O and ‘en’ are of
the order of 1011, 1027, 1015 and 108 respectively. Then 97. In the silver plating of copper, K[Ag(CN)2] is used
(en = ethylene diamine) instead of AgNO3. The reason is
(a) less availability of Ag+ ions, as Cu cannot displace
(a) en is the strongest ligand –
Ag from [Ag(CN)2] ion
(b) these values cannot predict the strength of the
(b) more voltage is required
ligand
– (c) a thin layer of Ag is formed on Cu
(c) CN is the strongest ligand
(d) Ag+ ions are completely removed from solution
(d) all ligands are equally strong
20.28 Chapter 20
98. Which of the following will exhibit geometrical isom- 104. Predict the correct statement about A and B in the
erism? (M stands for a metal, and a and b are achiral above question?
ligands, (1) A is diamagnetic and B is paramagnetic with two
(1) Ma2b2 (2) Ma4b2 unpaired electrons
(3) Ma5b (4) Ma6 (2) A is diamagnetic and B is paramagnetic with one
(a) 1 and 2 (b) 2 and 3 unpaired electron
(c) 1 and 3 (d) 2 and 4 (3) The hybridization of A and B are dsp2 and sp3
+
99. Why is [Ni(en)3]2 , nearly 1010 times more stable than respectively
+
[Ni(NH3)6]2 ? (en = enthlene diamine) (4) The hybridization of A and B are sp3 and dsp2
(a) NH3 is the weakest ligand respectively
(b) ‘en’ is a chelating ligand and forms thermody (a) 1 and 3 (b) 2 and 4
namically more stable complexes (c) 2 and 3 (d) 3 and 4
(c) six NH3 ligands cause steric hindrance around the 105. In the complex [Cu(CN)4]3– the hybridization state,
+
Ni2 centre oxidation state and number of unpaired electrons
(d) NH3 evaporates easily and causes instability to are
+
the [Ni(NH3)6]2 complex (a) dsp2, +1, 1 (b) sp3, +1, zero
100. When concentrated HCl is added to a solution of (c) sp , +2, 1
3
(d) dsp2, +2, zero
+
[Co(H2O)6]2 ion, an intense blue colour devel-
ops due to the formation of which one of the 106. Consider the following complex [Cr(NH3)5CO3]ClO4
following? The coordination number, oxidation number, number
– – of d electrons and number of unpaired d electrons on
(a) [CoCl4]2 (b) [CoCl6]4
+ the metal are, respectively
(c) [CoCl(H2O)5] (d) [CoCl2(H2O)4]
(a) 6, 3, 6, 0 (b) 6, 3, 6, 3
(c) 6, 0, 6, 3 (d) 6, 2, 6, 3
101. Which one of the following complexes is diamagnetic
– –
in nature? 107. Among [Ni(CO)4], [Ni(CN)4]2 and [NiCl4]2
(1) K2[Ni(CN)4] (2) [Ni (H2O)6] (NO3)2 –
(a) [Ni(CO)4] and [NiCl4]2 are diamagnetic and
(3) [Co(NH3)6] Cl3 (4) [Pt (NH3)4] Cl2 –
[Ni(CN)4]2 is paramagnetic
Select the correct answer – –
(b) [NiCl4]2 and [Ni(CN)4]2 are diamagnetic and
(a) 1 and 2 (b) 2 and 3
(c) 1, 2 and 4 (d) 1, 3 and 4 [Ni(CO)4] is paramagnetic
– –
102. The oxidation number of Fe in [Fe(CN)6]4 , Cr in (c) [Ni(CO)4] and [NiCN4]2 are diamagnetic and
–
[Cr(NH3)3 (NO2)3] and Ni in [Ni(CO)4] are respectively [Ni(Cl)4]2 is paramagnetic
(a) 0, +3, +2 (b) +3, +3, 0 –
(c) +3, 0, +3 (d) +2, +3, 0 (d) [Ni(CO)4] is diamagnetic and [NiCl4]2 and
–
[Ni(CN)4]2 are paramagnetic
103. The coordination number of Ni2+ is 4.
NiCl2 + KCN (excess) A (Cyano complex) 108. Consider the following spatial arrangements of the
octahedral complex ion [Co(NH3)4 Cl2] .
+
NiCl2 + conc. HCl (excess) B (chloro com-
plex) The IUPAC name of A and B are
Cl
(a) potassium tetracyanonickelate (II), potassium tetra- NH3
H3 N Cl H 3N Cl
chloronickelate (II) Co Co
(b) tetracyanopotassiumnickelate (II), H 3N NH3 Cl NH3
tetrachloropota−ssiumnickelate(II) NH3 NH3
(c) tetracyanonickel(II), tetrachloronickel(II) (1) (2)
(d) potassium tetracyanonickel(II), potassium
tetra−chloronickel(II)
Cl (c) 4 < 1 < 2 < 3 (d) 3 < 1 < 4 < 2

NH3
Cl NH3
H3N Cl 112. Each of the compounds Pt (NH3)6Cl4, Cr(NH3)6Cl3,
Co Co
H 3N
Co(NH3)4Cl3 and K2PtCl6 has been dissolved in water
NH3 H3N
NH3
NH3 to make its 0.001 M solution. The order of their
Cl
increasing conductivity in solution is
(3) (4)
(a) K2PtCl6 < Pt(NH3)6Cl4 < Cr(NH3)6Cl3 <
Which of the following statements is incorrect Co(NH3)4Cl3
regarding these structures? (b) Cr(NH3)6Cl3 < Co(NH3)4Cl3 < Pt(NH3)6Cl4 <
(a) 2 and 3 are cis and trans isomers respectively K2PtCl6
(b) 1 and 3 are enantiomers
(c) Co(NH3)4Cl3 < K2PtCl6 < Cr(NH3)6Cl3 <
(c) 3 and 4 have identical structures
Pt(NH3)6Cl4
(d) 2 and 4 are trans and cis isomers respectively
(d) Pt(NH3)6Cl4 < K2PtCl6 < Co(NH3)4Cl3 <
109. Which of the following pairs of isomers and types of Cr(NH3)6Cl3
isomerism are correctly matched?
(1) [Co(NH3)5(NO2)]Cl2 and [Co(NH3)5 (ONO)]Cl2 113. Arrange the following in order of decreasing number
of unpaired electrons:
Linkage isomers + –
1. [Fe(H2O)6]2 2. [Fe(CN)6]3
(2) [Cu(NH3)4] [PtCl4] and [Pt(NH3)4] [CuCl4] – +
3. [Fe(CN)6]4 4. [Fe(H2O)6]3
Co-ordinationIsomers
(3) [Pt(NH3)4 Cl2] Br2 and [Pt(NH3)4 Br2] Cl2 (a) 4, 1, 2, 3 (b) 1, 2, 3, 4
(c) 4, 2, 1, 3 (d) 2, 3, 1, 4
Ionisation Isomers
Select the correct answer using the codes given below: 114. Match the list I and II, pick the correct matching from
(a) 1 and 2 (b) 2 and 3 the codes given below
(c) 1 and 3 (d) 1, 2 and 3 List I List II
–
(a) [Ag(CN)2] 1. square planar and 1.73 BM
110. The correct order of magnetic moment (spin only val- –
ues in BM) among the following is (b) [Cu(CN4)]3 2. linear and zero
–
– – – (c) [Cu(CN)6] 3
3. octahedral and zero
(a) [MnCl4]2 > [CoCl4]2 > Fe(CN6)4 +
– –
(d) [Cu(NH3)4]2 4. tetrahedral and zero
(b) [Fe(CN)6]4 > [MnCl4]2 > [CoCl4]2– (e) [Fe(CN)6]4
–
5. octahedral and 1.73 BM
– –
(c) [Fe(CN)6]4 > [CoCl4]2 > [MnCl4]2– (a) a-4, b-2, c-5, d-3, e-1
– – –
(d) [MnCl4]2 > [Fe(CN)6]4 > [CoCl4]2 (b) a-4, b-5, c-2, d-1, e-3
(Atomic number of Mn = 25, Fe = 26, Co = 27, Ni = 28) (c) a-2, b-4, c-5, d-1, e-3
111. Select the correct increasing order of 10 Dq value for (d) a-5, b-4, c-1, d-3, e-2
chromium complexes using the given codes – –
+ –
115. In the complexes [Cr(CN)6]3 , [CuCl4]2 , [Cu(NH3)2]+.
(1) [Cr(en)3]3 (2) [Cr(ox)3]3 The number of unpaired electrons are respectively
– +
(3) [CrF6]3 (4) [Cr (dtc)]3
(a) 1, 3 and 0 (b) 3, 2 and 1
(Here, dtc = dithiocarbamate)
(c) 3, 2 and 0 (d) 3, 1 and 0
(a) 1 < 2 < 3 < 4 (b) 3 < 4 < 2 < 1
More than One Option Correct Type
116. Which of the following are paramagnetic tetrahedral (a) [FeCl4]− (b) [Ni(CN)4]2−
species? (c) [NiCl4]2− (d) [Zn(NH3)4]2+
20.30 Chapter 20
117. Which of the following are diamagnetic? (a) Shape is tetrahedral

(b) Hybridization state of central ion is sp3
(a) [Ni (H2O)6]2+ (b) [Zn(NH3)4]2+
(c) Effective atomic number of central ion is 35
(c) [Ni (CN)4]2– (d) [Co(NH3)6]3+ (d) Number of unpaired electrons present in the cen-
118. The proposed complex with the nomenclature chlo- tral ion is 1
rodiaquatriammine cobalt (III) chloride can be repre- 121. Identify the coordination compounds
sented wrongly as
(a) FeSO4.(NH4)2SO4.6H2O
(a) [CoCl(NH3)3 (H2O)2]Cl2 (b) Fe(CN)2.4KCN
(b) [Co(NH3)3 (H2O) Cl3] (c) KCl.MgCl2.6H2O
(c) [Co(NH3)3 (H2O)2 Cl2 ] Cl (d) CuSO4.4NH3
(d) [Co(NH3)3 (H2O)3] Cl3
122. The main draw back of valence bond theory is/are
119. Which of the following statements is/are correct
(a) It cannot explain magnetic properties of co-ordi-
regarding metal carbonyl?
nation compounds
(a) In Fe3(CO)12 no. of Fe – Fe bonds are 3 (b) It cannot distinguish between high spin and low
(b) In Mn2(CO)10 bond order of Mn – Mn is 0 spin complex
(c) Fe(CO)5 is diamagnetic (c) It does not provide an answer to the origin of
(d) In Fe2(CO)4 all bond length are same characteristic colours of complex ions
120. For the complex [Cu(NH3)4]2+ (d) It is a qualitative approach
Passage Based Questions

Passage-1 depending upon nature and magnetic field of ligands are either
stabilized or destabilized. The energy difference between the
The coordination compound is a complex substance which
two sets whenever lies in the visible region of the electromag-
contains a central metal atom or ion surrounded by oppo-
netic spectrum, then the electronic transition t2g eg are
sitely charged ions or neutral molecules. These compounds
responsible for colours of the coordination compounds
exhibit structural as well as stereoisomerism. Hybridisation
theory explains the geometry of the complex. Crystal field 125. Ti3+(aq) is purple while Ti4+(aq) is colourless because
theory explains the colour of complexes and magnetic
(a) The difference between t2g and eg of Ti4+ is quite
properties.
high and does not fall in visible region.
123. Which one of the following does not show optical (b) There is no crystal field effect in Ti4+
activity? (c) Ti4+ has d0 configuration.
(a) [Cr(NH3)4Cl2]+ (d) Ti4+ is very small ion than Ti3+ and does not adsorb
(b) [Pt(Br)(Cl)(I)(NO2)(C6H5N)(NH3)]− any radiation.
(c) Cis[Co(en)(NH3)2Cl2]+ 126. Which of the following colour is not due to d-d tran-
(d) Cis[Co(en)2Cl2] + sition of
(a) Yellow colour of CdS.
124. Identify the correct statement
(b) Red colour of blood
(a) [Ni(CN)4]2− is tetrahedral and paramagnetic (c) Orange colour of Cr2O72− in acidic medium.
(b) [NiCl4]2− is square planar and paramagnetic (d) Both (a) and (c).
(c) [Ni(CO)4] is square planar and paramagnetic
127. Which of following complex ions will be coloured in
(d) [Cu(CN)4]3− is tetrahedral and diamagnetic aqueous state?
Passage-2 (a) [Ni(CN)4]2−
(b) [Ni(H2O)6]2+
When degenerate d-orbitals of an isolated atom/ion are
brought under the impact of magnetic field of ligands, the (c) [Sc(H2O)6]3+
degeneracy is lost. The two newly formed sets of d-orbitals, (d) Both (b) and (c)
Match the Column Type

128. Match the following 131. Match the following
Column–I Column–II Column–I Column–II
(a) [Zn(NH3)4]2+ (p) d2sp3 (a) [MnCl6]3− (p) One unpaired electron
(b) [Cu(CN)4]3− (q) sp3 (b) [Fe(CN)6]3− (q) d2sp3
(c) [Co(NO2)6]3− (r) Number of unpaired (c) [CoF6]3− (r) sp3d2
electrons is zero
(d) [Fe(H2O)6]2− (s) Four unpaired electrons
(d) [FeCl4]− (s) Paramagnetic
(t) Three unpaired electrons
(t) Diamangetic
132. Match the following
Column–I Column–II
(a) [Co(NH3)4(H2O)2] (p) Geometrical isomers
(a) [Co(NO2)2(H2O)2(NH3)2] (p) Number of Cl2
NO3 stereoisomers
(b) [Pt(NH3)2Cl2] (q) Paramagnetic
=6
(b) [Ni(en)3]Br3 (q) Linkage (c) [Co(H2O)5Cl]Cl (r) Diamagnetic
isomerism (d) [Ni(H2O)6]Cl2 (s) Metal ion with +2
(c) [Co(NH3)3(py)3]Br2 (r) Ionization oxidation state
isomerism (t) sp3d2 hybridization
(d) [Pt(en)(SCN)2] (NO3)2 (s) Optical of central metal atom
isomerism
(t) Geometrical
isomerism Column–I Column–II
130. Match the following (a) [Ni(CN)4]2− (p) Octahedral
(b) [MnF6]4− (q) Paramagnetic
Column–I (Inorganic ions) Column–II (can
get tested using (c) [Fe(CN)6]3− (r) Square planar
reagent) (d) [Cr(H2O)6] 3+
(s) d2sp3 hybridization
(a) Co2+ (p) K4[Fe(CN)6] (t) Weak field ligand.
(b) Cu 2+
(q) KSCN 134. Match the following
(c) Fe 3+
(r) K3[Fe(CN)6]
(d) Zn2+ (s) KNO2 + (a) Na2[Pt(SCN)4] (p) Ionisation
CH3CO2H isomerism
(t) K2[Hg(SCN)4] (b) [CrCl2(NH3)4]NO3 (q) Linkage isomerism
(c) [Pt(NO2)(gly) (r) Geometrical
(NH3)] isomerism
(d) K3[Fe(OH)2(C2O4)2] (s) optical isomerism
(t) hydrate isomerism
Integer Type
135. The mineral (A) is [CuCl2.xCu(OH)2]. A 45.05 ml pletely with 1.6320 g of the compound (A) whose
solution of 0.5089 M HCl was required to react com- molar mass is 427. Hence, x is _______
20.32 Chapter 20
136. 14..How many milliliters of 0.05 M K4[Fe(CN)6] 141. Amongst the following, the total number of species
solution are required for titration of 60 ml of 0.01 which are diamagnetic is _______.
M ZnSO4 solution, when the product of reaction is
K4[Fe(CN)6], K3[Cr(CN)6], K3[Co(CN)6],
K2Zn3[Fe(CN)6]2 ?
K2[Ni(CN)4], [Co(NH3)6]3+, K2TiF6[Pt(NH3)4]2+
137. For the coordination compound PtCl4.5NH3, the
charge on cation is found to be +3. How many ions 142. The possible number of co-ordination isomers of
are furnished on ionization of the complex? Pt(Py)4CuCl4 are ______.
138. In the complex Fe(CO)x, the value of x is _____. 143. When excess of KCN is added to aqueous solu-
(Fe = 26) tion of copper sulphate a co-ordination compound
Kx[Cu(CN)4] is formed. The value of x is
139. Na2O has antifluorite structure. The coordination
number of oxide ion is ______. 144. The number of viable coordination isomers possible
for the complex [Pt(NH3)4][CuCl4] should be ?
140. The number of geomatrical isomers exhibited by
Cr(NH3)3Cl3 is ______. 145. The number of unpaired electrons in the complex ion
[CoF6]3− is
Previous Year’s Questions
146. In [Cr(C2O4)3]3– , the isomerism shown is [2002] 151. In the coordination compound K4[Ni(CN)4], the oxi-
(a) optical dation state of nickel is [2003]
(b) ionization (a) –1 (b) 0
(c) geometrical (c) +1 (d) +2
(d) ligand
152. A mole of complex compound Co(NH3)5Cl3 gives 3
147. In the complexes [Fe(H2O)6]3+, [Fe(CN)6]3–, [2002] mole of ions, when dissolved in water. One mole of
the same complex reacts with two mole of AgNO3
[Fe(C2O4)3]3– and [FeCl6]3–, more stability is shown by solution to form two mole of AgCl (s). The structure
(a) [FeCl6]3– (b) [Fe(C2O4)3]3– of the complex is [2003]
(c) [Fe(CN)6]3– (d) [Fe(H2O)6]3+ (a) [Co(NH3)3 Cl3].2NH3
(b) [Co(NH3)5 Cl].Cl2
148. A similarity between optical and geometrical isomer-
ism is that [2002] (c) [Co(NH3)4 Cl2]Cl.2NH3
(d) [Co(NH3)4 Cl2]Cl2.2NH3
(a) if in a compound one is present then the other will
also be present 153. Coordination compounds have great importance in
(b) each gives equal number of isomers for a given biological systems. In this context, which of the fol-
compound lowing statements is incorrect? [2004]
(c) both are included in stereo isomerism (a) chlorophylls are green pigments in plants and
(d) they have no similarity contain calcium
149. A square planar complex is formed by hybridization (b) haemoglobin is the red pigment of blood and con-
of which atomic orbitals? [2002] tains iron
(c) cyanocobalamin is vitamin B12 and contains
(a) s, px, py, dx – y
2 2
cobalt
(b) s, px, py, dyz
(d) carboxypeptidase-A is an enzyme and contains
(c) s, px, py, dz2
zinc
(d) s, px, py, dxy
154. Which one of the following has largest number of iso-
150. The type of isomerism present in nitropentaamine
mers? [2004]
chromium (III) chloride is [2002]
(a) [Ru (NH3)4 Cl2]+ (b) [Co(NH3)5Cl]2+
(a) ionization (b) optical
(c) [Ir (PR3)2 H (CO)]2+ (d) [Co (en)2 Cl2]+
(c) polymerization (d) linkage
[R = alkyl group, en = ethylenediamine]
155. The correct order of magnetic moments (spin only 162. The value of ‘spin only’ magnetic moment for one of
values in B.M.) among the following is [2004] the following configurations is 2.84 BM. The correct
(Atomic number of Mn = 25, Fe = 26, Co = 27 ) one is [2005]
(a) d (in strong ligand field)
4
(a) [MnCl4]2– > [CoCl4]2– > [Fe(CN)6]4–
(b) d4 (in weak ligand field)
(b) [MnCl4]2– > [Fe(CN)6]4– > [CoCl4]2– (c) d3 (in weak as well as in strong fields)
(c) [Fe(CN)6]4– > [MnCl4]2– > [CoCl4]2– (d) d5 (in strong ligand field)
(d) [Fe(CN)6]4– > [CoCl4]2– > [MnCl4]2–
163. The IUPAC name for the complex [Co(NO2)(NH3)5]
156. Which one of the following complexes is an outer Cl2 is [2006]
orbital complex? [2004] (a) nitrite-N-pentaamminecobalt(III) chloride
(a) [Co(NH3)6]3+ (b) nitrite-N-pentaamminecobalt(II) chloride
(b) [Fe(CN)6]4– (c) pentaamminonitrite-N-cobalt(II) chloride
(c) [Ni(NH3)6]2+ (d) pentaamminonitrite-N-cobalt(III) chloride
(d) [Mn(CN)6]4– 164. Nickel (Z = 28) combines with a uninegative
monodentate ligand X– to form a paramagnetic
157. The coordination number of a central metal atom in a complex [NiX4]2–, the number of unpaired
complex is determined by [2004] electrons in nickel and the geometry of this
(a) the number of only anionic ligands bonded to the complex ion is [2006]
metal ion (a) one, tetrahedral (b) two, tetrahedral
(b) the number of ligands around a metal ion bonded (c) one, square planar (d) two, square planar
pi-bonds
(c) the number of ligands around a metal ion bonded 165. In Fe(CO)5, the Fe–C bond possesses [2006]
by sigma and pi-bonds (a) π-character only
(d) the number of ligands around a metal ion bonded (b) both σ and π characters
by sigma bonds (c) ionic character
(d) σ character only
158. The oxidation state of Cr in [Cr(NH3)4Cl2]+ [2005]
166. How many EDTA (ethylenediamine-tetraacetic acid)
(a) 0 (b) +1
molecules are required to make an octahedral com-
(c) +2 (d) +3
plex with a Ca2+ ion? [2006]
159. The IUPAC name of the coordination compound (a) six (b) three
K3[Fe(CN)6] is [2005] (c) one (d) two
(a) potassium hexacyanoferrate (II)
167. The ‘spin-only’ magnetic moment [in units of Bohr
(b) potassium hexacyanoferrate (III) magneton (μB)] of Ni2+ in aqueous solution would be
(c) potassium hexacyanoiron (II) (Atomic number of Ni = 28) [2006]
(d) ripotassium acyanoiron (II) (a) 2.84 (b) 4.90
160. Which of the following compounds shows optical (c) 0 (d) 1.73
isomerism? [2005] 168. Which one of the following has a square planar geom-
(a) [Cu(NH3)4] 2+
etry? [2007]
(b) [ZnCl4]2– (a) [FeCl4]2–
(b) [NiCl4] 2–
(c) [Cr(C2O4)3]3– (c) [PtCl4]2– (d) [CoCl4]2–
(d) [Co(CN)6]3–
169. The coordination number and the oxidation state of
161. Which one of the following cyano complexes the element ‘E’ in the complex [E(en)2 (C2O4)]NO2
would exhibit the lowest value of paramagnetic
behaviour? [2005] (Here (en) is ethylene diamine) are, respectively,
[2008]
(a) [Cr(CN)6] 3–
(a) 6 and 2 (b) 4 and 2

(b) [Mn(CN)6]3–
(c) 4 and 3 (d) 6 and 3
(c) [Fe(CN)6]3–
(d) [Co(CN)6]3–
20.34 Chapter 20
170. In which of the following octahedral complexes 176. Which of the following facts about the complex
of Co (Atomic number 27), will the magnitude of ∆° [Cr(NH3)6]Cl3 is wrong? [2011]
be the highest? [2008] (a) The complex gives white precipitate with silver
(a) [Co(CN)6] 3–
(b) [Co(C2O4)3] 3–
nitrate solution.
(c) [Co(H2O)6]3+ (d) [Co(NH3)6]3+ (b) The complex involves d2sp3 hybridisation, and is
octahedral in shape.
171. Which of the following has an optical isomer? [2009]
(c) The complex is an outer orbital complex.
(a) [CO(en) (NH3)2]2+ (d) The complex is paramagnetic.
(b) [CO(H2O)4 (en)]3+
(c) [CO(en)2 (NH3)2]3+ 177. Which among the following will be named as
(d) [CO(NH3)3 Cl]+ dibromidobis (ethylene diamine) chromium
(III) bromide? [2012]
172. Which of the following pairs represents
(a) [Cr(en)2Br2]Br (b) [Cr(en)Br2]Br
linkage isomers? [2009]
(c) [Cr(en)3]Br3 (d) [Cr(en)2Br2]Br
(a) [Pd (P Ph3)2 (NCS)2] and
[Pd (P Ph3)2 (SCN)2] 178. Which of the following complex species is not
(b) [Co (NH3)5 NO3] SO4 and expected to exihibit optical isomerism? [2013]
[Co (NH3)5 SO4] NO3 (a) [Co(NH3)3Cl3] (b) [Co(en)(NH3)2Cl2] +
(c) [Pt Cl2(NH3)4] Br2 and (c) [Co(en)3]3+ (d) [Co(en)2Cl2]+

(d) [Cu (NH3)4] [Pt Cl4] and
179. The octahedral complex of a metal ion M3+ with four
[Pt (NH3)4] [CuCl4]
monodentate ligands L1, L2, L3 and L4 absorb wave-
173. Which one of the following has an optical isomer? length in the region of red, green, yellow and blue,
[2010] respectively. The increasing order of ligand strength
(a) [Zn(en) (NH3)2] 2+
(b) [Co(en)3] 3+
of the four ligands is: [2014]
(c) [Co(H2O)4 (en)]3+ (d) [Zn(en)2]2+ (a) L3 < L2 < L4 < L1
(en = ethylenediamine) (b) L1 < L2 < L4 < L3
(c) L4 < L3 < L2 < L1
174. A solution containing 2.675 g of CoCl3.6NH3 (molar
(d) L1 < L3 < L2 < L4
mass = 267.5 g mol–1) is passed through a cation
exchanger. The chloride ions obtained in solution 180. The pair having same magnetic movement is [2016]
were treated with excess of AgNO3 to give 4.78 g of (a) [Cr(H2O)6]2+ and [Fe(H2O)6]2+
AgCl (molar mass = 143.5 g mol–1). The formula of (b) [Mn(H2O)6]2+ and Cr(H2O)6]2+
the complex is (Atomic mass of Ag = 108 u) [2010] (c) [CoCl4]2- and [Fe(H2O)6]2+
(a) [Co (NH3)6] Cl3 (d) [Cr(H2O)6]2+ and [CoCl4]2-
(b) [CoCl2 (NH3)4] Cl
(c) [CoCl3 (NH3)3] 181. Which of the following complexe shows optical
(d) [CoCl (NH3)5] Cl2 isomerism [2016]
(a) Cis[Co(en)2Cl2]Cl
175. The magnetic moment (spin only) of (b) trans[Co(en)2Cl2]Cl
[NiCl4]2– is: [2011] (c) [Co(NH3)4Cl2]Cl
(a) 1.41 BM (b) 5.64 BM (d) [Co(NH3)3Cl3]
(c) 1.28 BM (d) 2.82 BM
ANSWER KEYS
Single Option Correct Type

1. (c) 2. (c) 3. (d) 4. (b) 5. (d) 6. (c) 7. (d) 8. (c) 9. (a) 10. (c)
11. (b) 12. (b) 13. (a) 14. (d) 15. (b) 16. (d) 17. (b) 18. (b) 19. (c) 20. (a)
21. (d) 22. (c) 23. (a) 24. (d) 25. (d) 26. (b) 27. (a) 28. (b) 29. (b) 30. (a)
31. (d) 32. (c) 33. (b) 34. (d) 35. (c) 36. (a) 37. (b) 38. (c) 39. (c) 40. (d)
41. (b) 42. (d) 43. (b) 44. (c) 45. (b) 46. (b) 47. (a) 48. (b) 49. (b) 50. (b)
51. (a) 52. (c) 53. (a) 54. (b) 55. (b) 56. (b) 57. (c) 58. (a) 59. (d) 60. (b)
61. (c) 62. (a) 63. (a) 64. (c) 65. (d) 66. (b) 67. (c) 68. (d) 69. (a) 70. (b)
71. (d) 72. (c) 73. (d) 74. (a) 75. (a) 76. (a) 77. (b) 78. (c) 79. (a) 80. (a)
81. (b) 82. (b) 83. (d) 84. (c) 85. (b) 86. (a) 87. (b) 88. (a) 89. (c) 90. (a)
91. (c) 92. (d) 93. (b) 94. (c) 95. (a) 96. (a) 97. (a) 98. (a) 99. (b) 100. (a)
101. (d) 102. (d) 103. (a) 104. (a) 105. (b) 106. (a) 107. (c) 108. (b) 109. (d) 110. (a)
111. (b) 112. (c) 113. (a) 114. (c) 115. (d)

116. (a) and (c) 117. (b), (c) and (d) 118. (b), (c) and (d) 119 (a) and (c)
120. (c) and (d) 121. (b) and (d) 122. (a), (c) and (d)

123. (a) 124. (d) 125. (c) 126. (d) 127. (b)
Match the Column Type

128. (a) → (q), (r), (t); (b) → (q), (r), (t); (c) → (p), (r), (t); (d) → (q), (s)
129. (a) → (p), (q), (r), (s); (b) → (s), (t); (c) → (s), (t); (d) → (q), (r)
130. (a) → (q), (s), (t); (b) → (p), (q), (r); (c) → (p), (q), (r); (d) → (p), (t)
131. (a) → (q), (t); (b) → (p), (q); (c) → (r), (s); (d) → (r), (s)
132. (a) → (p), (q), (s), (t); (b) → (p), (r), (s); (c) → (q), (s), (t); (d) → (q), (s), (t)
133. (a) → (r); (b) → (p), (q), (t); (c) → (p), (q), (s); (d) → (p), (q), (s), (t)
134. (a) → (q), (r); (b) → (p), (r); (c) → (q), (r); (d) → (r), (s)
Integer Type
135. (3) 136. (8) 137. (4) 138. (5) 139. (8) 140. (2) 141. (6) 142. (4) 143. (3) 144. (3)
145. (4)
Previous Year’s Questions

146. (a) 147. (b) 148. (c) 149. (a) 150. (d) 151. (d) 152. (b) 153. (a) 154. (d) 155. (a)
156. (c) 157. (d) 158. (d) 159. (b) 160. (c) 161. (d) 162. (a) 163. (d) 164. (b) 165. (b)
166. (c) 167. (a) 168. (c) 169. (d) 170. (a) 171. (c) 172. (a) 173. (b) 174. (a) 175. (d)
176. (c) 177. (a) 178. (a) 179. (d) 180. (a) 181. (a)
20.36 Chapter 20
HINTS AND SOLUTIONS
2. FeSO4 (NH4)2 SO4–6H2O Fe2+ + 2SO42– + 49. Octahedral complexes of the type [M(aa)2 x2] (here x =
+
2NH4 monodentate ligand and (aa) = didentate ligand) exhibit both
cis-trans isomerism and optical isomerism.
••
4. EDTA is C2H4 [N(CH2COO–)2]2 58. S atom is the donor in SCN and N atom is the donor in NCS.
It has six positions (that is, six electron pairs) available for The linkage isomerism arises when the ligand has two possi-
attachment at central metal atom. bilities to attach on central atom.
5. All are the required facts for diethyl triamine. 59. Ferrocene is a diphenyl iron complex.
6. CN– ion is at the extreme right but before CO in the spec- 60. 2 × a + 4 × (–2) + 2 × 0 + 2 × 0 = – 2
trochemical series. So it can cause maximum splitting of d a = + 3.
orbitals. 66. EAN = at. no. of central atom – oxidation state + 2x (no. of
8. [CoF6]3– forms outer orbital complex with sp3d2 hybridiza- ligands)
tion as F– has a weak ligand field. EAN = 78 – 4 + 2 × 6 = 86.
9. [Co(NH3)5Br]SO4 [Co(NH3)5Br]2+ + SO42– 68. The anion of the compound K3[Cr(C2O4)3] is [Cr(C2O4)3]3–
Pb + SO4
2+ 2–
PbSO4 ↓ or [Cr(ox)3]3–, here ox = C2O42–. Since such octahedral com-
White insoluble plexes have non-superimposable mirror images, so they
11. It involves sp3d2 hybridization. show optical isomerism.
13. [Cr(NH3)6]3+ has three unpaired electrons. 69. Here the complex compound [Co (en)2 Cl2]Br shows ioniza-
tion isomerism, cis-isomerism, trans-isomerism and optical
22. CN– is a stronger ligand according to spectrochemical series.
isomerism that is, have four isomers.
31. EAN = atomic number – oxidation number + 2 × CN
70. Cation with higher oxidation state has a larger value of
= 24 – 3 + 2 × 6 = 33
CFSE and CFSE decreases with the increase of the number
33. Electronic configuration of Fe in Fe(CO)5 is of d electrons.
3d 4s 4p 73. [Co(NO2)(SCN)(en)2]Br is an octahedral complex of the
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ×× ×××××× type [Mxy (aa)2]. This type of octahedral complexes show
dsp3 geometrical isomerism.
x x denotes the electron pair donated by CO. 75. As V(CO)6 contains 35 electrons so it does not obey
35. O2[PtF6] can be written as O2+[PtF6]–. The oxidation state of EAN rule.
Pt in this compound is +5. 76. MnO4– has no d electron.
Let X = oxidation state of oxygen 78. [Pt(NH3)4Cl]Cl3 [Pt(NH3)4 Cl]+ + 3Cl–
F = –1 80. The blue colour obtained in the Lassaigne’s test is due to the
So, 2X + 5 + 6 (–1) = 0 formation of Fe4[Fe(CN)6]3.
X=+½ 81. [MA5B] will not show geometrical isomerism.
37. The correct IUPAC name of Mn3 (CO)12 is given as 82. The coordination entity has four chloride ions, each having
Dodecacarbonyl trimanganese (0). a charge of –1, two neutral NH3 groups, and platinum metal
with an oxidation state of +4.
38. The complex formed represents finite dipole.
Let X = charge on coordination entity.
39. Both are tetrahedral with sp3 hybridization.
4 (–1) × 2 (0) + 4 = X
40. As all these are trans-forms, so no optical isomerism is
observed in them. X=0
42. Methyl lithium (Li–CH3) is an organometallic compound This shows that the coordination entity is not an ion and
due to the presence of M–C bond. hence, the formula of the tetrachloro diamine platinum(IV)
is [Pt(NH3)2 Cl4].
43. Cr3+: [Ar] 3d3
83. The complex compound [MCl2 Br2] SO4 gives [MCl2 Br
d2sp3 hybridization is present. Three unpaired d-electrons
SO4] Br as ionization isomer and also cis-isomers, trans-
are there.
isomers as geometrical isomers.
45. Fe2+ has d6 configuration and is expected to be the most para-
84. The complex having a higher value of the stability constant,
magnetic with four unpaired electrons.
is the most stable one.
46. Ag+ has d10 configuration with no unpaired electrons.
85. EAN of the central metal atom of [Fe(CN6)]3– and [Fe(CN)6]4– x + (3 × 0) + (–3) = 0
is not the same. x–3=0
86. Ag and Au is extracted by this process. x = +3
87. As for optical activity at least one bidentate ligand should be [Ni(CO)4]
there. x + (4 × 0) = 0
88. [Pt (NH3)5 Br] Br3 ionizes to [Pt (NH3)5 Br]3+ and x=0
3 Br– ions giving total four ions.
107. [Ni(CO)4] and [NiCN4]2– are diamagnetic (no unpaired elec-
89. CN– is the strongest ligand which gives the highest value of trons) while [Ni(Cl)4]2– is paramagnetic with two unpaired
the stability constant here 1027. electrons.
96. Cobalt assumes sp3d2 hybrid state and the number of unpaired 110. [Fe(CN)6]4– is an inner orbital complex, that is, it has d2sp3
electron in Co3+ is 4. hybridization with no unpaired electrons.
97. Due to less availability of Ag+ ions, as Cu cannot displace Ag [MnCl4]4– is a tetrahedral complex (sp3) with 5 unpaired
from [Ag(CN)2]– ion. electrons.
101. As [Ni (H2O)6] (NO3)2 has two unpaired electrons, so it will [CoCl4]2– is a tetrahedral hybridization (sp3) with two
be paramagnetic, while rest complexes are diamagnetic in unpaired electrons.
nature as they do not have any unpaired electron.
112. The conductivity of the solution increases as the number of
102. [Fe(CN)6]4– ions increase. Number of free ions in Co(NH3)–4 Cl3, K2PtCl6,
x + (–6) = –4 Cr(NH3)6Cl3 and Pt(NH3)6Cl4 are 1, 2, 3 and 4 respectively.
x = +2 Increasing conductivity order is 1 < 2 < 3 < 4.
[Co(NH3)3 (NO2)3] 113. 4, 1, 2 and 3 have 5, 4, 1 and 0 number of unpaired electrons
respectively.

116. [FeCl4]− 119.
Fe3+ 3d5 4s0. Cl− is a weak ligand. Hence sp3 hybridization
occurs. This gives tetrahedral geometry. It is paramagnetic
having 5 unpaired electrons.
[Ni(CN)4]2−
Ni2+ 3d8 4s0. CN− is a strong ligand. Electron pairing takes
place and dsp2 hybridization occurs. It is diamagnetic having
square planar geometry and has no unpaired electron.
[NiCl4]2−
Ni2+ 3d8 4s0. Cl− is a weak ligand. sp3 hybridization occurs. Iron is in zero oxidation state and dsp3 hydrobised state hav-
It has tetrahedral geometry and is paramagnetic as it has 2 ing all orbital are paired.
unpaired electrons.
[Zn(NH3)4]2+
Zn2+ 3d10 4s0. sp3 hybridization occurs. The complex is tetra-
hedral but is diamagnetic as it has no unpaired electron.

123. [Cr(NH3)4Cl2]+ has no chiral centre and hence is not optically 127. In (b), weak ligands form high spin complex. The unpaired
active electrons in d-orbital imparts colour due to d-d transition.
125. Because of empty d-orbital there is no d-d transition and
hence, Ti4+ is colourless.
20.38 Chapter 20
Integer Type
135. In CuCl2 xCu(OH)2, OH− is neutralised by HCl 140. MA3B3 type complexes have two geometrical isomers.
1.632 45.05 × 0.5089 141. [Fe(CN)6]4−, [Co(CN)6]3−
× 2x = [Ni(CN)4]2−, [Co(NH3)6]3+, [TiF6]2−
427 1000
x=3 [Pt(NH3)4]2+ all are diamagnetic
136. The required reaction is 142. [Pt(Py)4][CuCl4]
3ZN2+ + 2K4[Fe(CN)6] → K2Zn3[Fe(CN)6]2 + 6K+ [Pt(Cl)(Py)3] [CuCl3(Py)]
n=2 n=3 [CuCl(Py)3] [PtCl3(Py)]
[Cu(Py)4] [PtCl4]
Milliequivalents of Zn2+ = Milliequivalents of
K4 [Fe(CN)6] 143. 2KCN + CuSO4 Cu(CN)2 + K2SO4
60 × 0.01 × 2 = V × 0.05 × 3 2Cu(CN)2 Cu2(CN)2 + (CN)2
60 × 0.01 × 2 (unstable)
V= = 8ml.
0.053 Cu2(CN)2 + 6KCN 2K3[Cu(CN)4]
137. PtCl4.5NH3 [Pt(NH3)5 Cl] Cl3 144. [Pt(NH3)3Cl]+1[Cu(NH3)Cl3]−1,
↓ [Cu(NH3)3Cl]+1[Pt(NH3)Cl3]−1,
[Pt(NH3)5 Cl]+ + 3Cl– [Cu(NH3)4]+2[PtCl4]−2 are the three viable coordination iso-
138. In metal carbonyls, EAN rule is obeyed perfectly. mers. [Pt(NH3)2Cl2][Cu(NH3)2Cl2] is not a valid coordina-
For Fe(CO)x, EAN value is 36. tion isomer due to lack of possible charges on the complex.
145. Configuration of Co = 3d74s2
36 = 26 − 0 + 2(x)
Configuration of Co+3 = 3d6
x=5
Number of unpaired electron =
139. In the antifluorite structure, oxide ions form CCP lattice with
4
Na+ ions occupying tetrahedral voids. Hence the coordina-
tion no. of oxide is 8. That is, each O2− ion is surrounded by
eight Na+ ions and each Na+ ion is surrounded by four oxide
ions.
Previous Years’ Questions

146. Optical isomerism is shown by [Cr(C2O4)3]3– ion. There are no unpaired electrons, so the least value of para-
147. Complex having more rings in the structure will be more magnetic behaviour is observed.
stable. 162. If magnetic moment is 2.84 BM, the number of unpaired
148. Both optical and geometrical isomerism are the types of electrons will be 2.
stereo-isomerism. 168. All the complexes of Pt2+ are square planar including those
149. A square planar complex is formed by hybridization of s, px, with weak filed ligand such as halide ions.
py, d x2 – y2 atomic orbitals of the metal.
en
150. [Cr (NH3)5 (NO2] Cl2 shows linkage isomerism. It also shows
ionization isomerism.
153. Chlorophyll contains Mg. 169.
154. [Co(en)2Cl2] forms optical and geometrical isomers. E ox NO2
158. [Cr(NH3)4 Cl2]+

x = 4 × 0 + 2 × (–1) = +1
x–2 =1 en
x = +3
Here coordination number = 6 and oxidation
159. K3[Fe(CN)6] number = 3.
Potassium hexacyanoferrate (III) 160. As CN– is stronger ligand so it has ∆° highest.
161. [Co(CN)6]3– 171. It is an octahedral complex of the type [M (AA)2 X2] and
Co [Ar] 3d7 4s2 capable of showing optical isomerism
Co 3+
[Ar] 3d6 4s0
172. NCS– is an ambidentate ligand and it can be linked through Number of moles of AgCl formed = 3 × number of moles of
N or S so it is capable of showing linkage isomerism the complex
173. Square planar complexes of Zn2+ cannot show optical isom- The formula of the complex is [Co(NH3)6]Cl3
erism, So, options (A) and (D) are ruled out. 175. Ni2+ = [Ar] 3d84s0
2+ As the hybridization of central metal ion is sp3 in NiCl4–2.
+2 1+ Therefore number of unpaired electrons = 2.
µ = n(n+2)= 2 × 4 =2 2
&R
= 2 × 1.41 = 2.82 BM.
+2 1+ 176. Here the complex involves d2sp3 hybridisation, and hence it
2+ is an inner orbital complex.
177. [Cr(en)2Br2]Br
will have two planes of symmetry, so it optically inactive.
dibromobis ethylenediamine chromium (III) bromide
Thus optically active compound is
178. [Co(NH3)3 Cl3] is a [Ma3b3] type of complex, so it can’t show
1+ optical isomorism.
+1 1+ 180. As Both cr2+ and fe2+ have same No. of un–pairede i.e 4
Cr2+ → 3d4
&R fe2+ → 3d6
181. Cis [Co(en)2Cl2]Cl can show optical isomeric
+1 1+
1+ en + en
en Co Cl
—
Co en l
As it has no plane of symmetry. so it is optically active. Cl Cl Cl Cl
2.675 Mirror
174. Number of moles of the complex = = 0.01
267.5
4.78
Number of mole of AgCl formed = = 0.03
143.5

Coordination Compounds

Uploaded by

Copyright:

Available Formats

Coordination Compounds

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Coordination Compounds

Uploaded by

Copyright:

Available Formats

CHAPTER

TERMS RELATED TO A COMPLEX

Table 20.1 Effective Atomic Numbers

(+) or d-K3[Ir (C2O4)3] is potassium (+) or d-trioxa- [Cr(en)3]Cl3 d or l tris(ethylenediamine)

(a) [Co(NH3)5 SO4]Br Red colour For example,

3. [CoCl3(H2O)3] 3H2O and

Stereo Isomerism • Mabcd type square planar complexes exists in three

For example, [Pt (gly)2 ] Co en Co en

H2C Pt CH2 Cl NH3

• Octahedral complexes of the type M(aa)2b 2,

Optical isomerism For example, [Co (en)3]3+

Secondary valency Valence Bond Theory

• Secondary valency cannot be obtained in free state 1 sp Linear [CuCl2],

[Co (NH3)5 Cl] Cl2 + AgNO3 Here, 2 moles planar [PdCl4] ,

of AgCl are precipated as follows: [Cu(NH3)4] ,

2Cl– + 2Ag+ 2AgCl [Pt(NH3)4]

For example, [Ni(CN)5]

Table 20.3 Physical Properties of Ammine Complexes

2 PtCl4.5NH3 3 410 4 [Pt(NH3)5 Cl]Cl3

3 PtCl4.4NH3 2 240 3 [Pt(NH3)4 Cl2]Cl2

5 PtCl4.2NH3 0 0 – [Pt(NH3)2 Cl4]

(iii) sp3d2 hybrid orbitals of Fe2+ ion Cr

(ii) Co3+ ion

(i) Ni atom (v) dsp2 hybrid orbitals in [Cu(CN)4]2–

↑↓ ↑↓ ↑↓ ↑↓ ×××××××× (vii) It has no unpaired electron, that is, n = 0, μ = 0. Hence,

• As the five d orbitals of an isolated gaseous element 2. When ∆o < P

(t2 + eg) orbitals

Octahedral complex t Applications of crystal field theory

(t2 + eg) orbitals

• In the test of Ni2+ using DMG (Dimethyl glyoxi- Preparation

Types of Organometallic Compounds

σ-bonded organometallic compounds

Zeisse’s salt, K[PtCl3 (η2–C2H4)] Structure and bonding in metal carbonyl

For example, Figure 20.30 Structure of Facial or Fac-Isomer

CH3 CH3 H3C H3C

Figure 20.29 Bis(benzoylacetonato)beryllium(II) d-and l- forms of

 K3[Co(NO2)6] that is potassium hexanitrocobaltate (III) is

Single Option Correct Type

1:4) is found to have effective molarity of 0.02 M of Cr = 24] is

3+ 58. [(C6H5)2 Pb (SCN)2] and [(C6H5)2 Pb (NCS)2] are

H3C H3C (a) Tridendate (b) 1, 10-phenanthroline

85. In which of the following pairs, the EAN of the cen- +

(d) cis-[Co (en)2 Cl2]+ (b) [Co(NH3)6]2

Cl (c) 4 < 1 < 2 < 3 (d) 3 < 1 < 4 < 2

More than One Option Correct Type

117. Which of the following are diamagnetic? (a) Shape is tetrahedral

Passage Based Questions

Match the Column Type

Previous Year’s Questions

(a) 6 and 2 (b) 4 and 2

(c) [Pt Cl2(NH3)4] Br2 and (c) [Co(en)3]3+ (d) [Co(en)2Cl2]+

Single Option Correct Type

More than One Option Correct Type

Passage Based Questions

Match the Column Type

Previous Year’s Questions

HINTS AND SOLUTIONS

More than One Option Correct Type

Passage Based Questions

Previous Years’ Questions