Reconstruct Your Chemistry With Prince Sir

CHEMISTRY
COORDINATION COMPOUNDS & ORGANOMETALLICS

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THEORY SHEET
Addition Or Molecular Compounds:
These are the compounds which are formed by the combination of two or more
simple salts.

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These can be divided into two categories:
(i) Double Salts (ii) Complex or Co-ordination compounds.

Double Salt

c e
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These molecular compounds exist only in crystal lattices & break down into their
constituent compounds when dissolved in water. for eg.

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K2SO4 + Al2 (SO4)3 + 24H2O)  K2SO4 . Al2 (SO4)3. 24H2O
Potash alum

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Coordination compounds or complex Compounds
Coordination compounds or (complex) are the compounds in which the central
metal atom is linked to a no. of ions or neutral mol’s by coordinate bonds.

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Double Salt Complex Compound.

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1. They usually contain two They are formed from simple salts
simple salts in which may or may not be
in equimolar proportions. equimolar proportions.

2. They dissociate completely The complex ion does not

into ions in the aqueous sol. dissociate into ions in aq. sol.

3. They are ionic compounds & They may or may not be

don’t contain ionic but the complex part always
any coordinate bond. contains coordinate bonds.

Some important terms used in coordination compounds

1. Ligands
The atoms, molecules or anions which donate a pair of e–s to the metal atom or ion
& form a co-ordinate bond with it are called ligands.

Types of ligands
* Unidentate Ligands :- A ligand which contain only one donor atom, it is called
unidentate ligands . eg

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 Reconstruct Your Chemistry With Prince Sir
-ively Charged ligands : F–, Cl –, Br– ,OH- , S2-,CN-etc.
+ively charged ligands : NO+
Neutral Ligands : CO, H2O , ROH, NH3, RNH2, R2NH , R3N

* Bidentate ligand :- If two donor atoms are there in a ligand, it is called a

bidentate ligand eg. CH2 – CH2 (en)

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COO– (ox) | |
| NH2 – Nh2
COO–
ethylene diamine

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* Multi or polydentate ligand  EDTA (ethylene diamine tetra acetic acid .

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CH2 — CH2 (Hexadentate)

c
| |

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N N
–
– CH2 COO

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OOCCH2 CH COO–
2 CH2 COO–

* Chelating Ligands :- The ligands which form a closed ring on bonding with the

P
central atom are called chelating complexes.
for e.g. Ethylene diammine(en), EDTA, Oxalate etc.

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* Denticity :- The no. of coordinating sites present in a ligand is called the denticity
of that ligand.

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Following table illustrates the types and structures of some common ligands

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 Reconstruct Your Chemistry With Prince Sir

Some Common Ligands

Name Formula Charge Name of Ligand

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e S
in c
P r
B y

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Name Formula Charge Abbreviation Donor Sites

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e S
in c
P r
B y

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* Coordination number . :- The total no. of coordinate bonds formed by ligands
to the central metal ion is called the coordination no. of the metal ion.

Typ e o f ligan d Coo rd in ation n u m b er

of e ach ligan d

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Mo n od e ntate 1
Bid e ntate 2
Tride n tate 3
h exad en tate 6

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* Coordination sphere :- The central atom & the ligands which are directly at-

c
tached to it are enclosed in square brackets & are collectively termed as coordi-
nation sphere or coordination entity.

in
* Oxidation No. or state :- The oxidation no. of the central atom is defined as the

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charge that it carries as calculated by assigning appropriate charges to the ligands
& equating the sum of the charges on the central atom & the ligands equal t o
the charge on the coordination sphere.

y P Coordination sphere/entity

[Ni (NH3)6] Cl2

Counter ions

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Coordination no.
Central Ligand
metal atom
Rules for writing formula of mononuclear co-ordination compounds

(1) Formula of the cation whether simple or complex is written first followed
by that of the anion.

(2) The coordination sphere is written in square brackets.

(3) The sequence of symbols within the coordination sphere is first the metal
atom followed by anionic ligands, then neutral ligands & finally cationic
ligands i.e.
[Metal atom  anionic  neutral  cationic ligands]

* If there are more than one anionic ligands, they are listed alphabetically
according to the first letter of their formulae. Same principle is followed for
neutral ligands or positive ligands.
for example NH3 and H2O, since H comes before N in alphabetical order so H2O
is written first .

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 Reconstruct Your Chemistry With Prince Sir
(4) Polyatomic ligands are enclosed in parentheses but all ligands are
formulated without any space in between.

(5) The no. of cations or anions to be written in the formula is calculated on

the basis that total +ve charge must be equal to the total –ve charge, as
the complex as a whole is electrically neutral.

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IUPAC NOMENCLATURE OF CO-ORDINATION COMPOUNDS

Rules for naming of Mononuclear Coordination compounds

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(1) Order of naming ions

The +ve ion (cation) whether simple or complex, is named first followed by

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the –ve ion (anion). The name is started with a small letter & the complex part

c
is written as one word. eg.
K2 [PtCl6] - potassiumhexachloroplatinate (1V)

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(2) Naming of ligands

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Different types of ligands are named as follows :-
(i)Negative ligands (org. or inorg.) end in – O, eg.

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CN– (cyano), NO2– (nitro), OH– (hydroxo).
If the name of the anionic ligand end in ide, ite or ate, the last ‘e’ is replaced
by ‘O’ giving – ido, ito, & ato

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_
e.g. SO4–2 (sulphato) ONO (nitrito)

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Cl- (Chlorido) Br (Bromido)
-
I-(Iodido)

(ii) Neutral ligands have no special ending but special names are given to
some ligands eg. NH3 (ammine), H2O (aqua), CO (carbonyl)

(iii) Positive ligands end in ‘ ium’

e.g. NO+ (nitrosonium), NO2+ (nitronium) etc.

(iv) Organic ligands :- They are given their own names.

e.g. CH3 (methyl), C2H5 (ethyl)

(v) In case of ambidentate ligands it is essential to specify the point of

attachment by plaing the symbol of the donor atom attached
after the name of the groups separted by hyphen. e.g.
— NO2, nitro, — ONO, nitrite
— SCN, thiocyanate, — NCS, isothiocyanate
[Co (ONO) (NH3)5] +2
Pentammine nitrito – O– cobalt (III)
[Co (NO2) (NH3)5] +2
Pentammine nitro–N–cobalt (III)

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(vi) Prefixes like di, tri, tetra etc. are used to indicate the no. of ligands.

(vii) Preference order:- All ligands whether –ve, neutral or +ve are arranged
alphabetically & named in this order.The prefixes di, tri etc. are not
to be considered while determining this alphabetical order.

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(viii) When the name of polydentate ligand already includes di, tri etc
eg. dipyridyl or ethylene diammine then bis, tris, tetrakis, pentakis
etc. are used instead of di, tri etc.

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(iX) With ligands like methyl amine also, the prefix bis is used to defferentiate
as if di is used, it makes it dimethylamine which is a different compound.

c e
(X) Naming of the coordination sphere :- Ligands are named first followed by the
metal atom :

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The end of the name of the metal depends upon the nature of the complex ion

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A. If the complex ion is a cation, the name of the central metal ion is
written as such followed by its oxidation state indicated by roman

P
numeral in parenthesis.

B. If the complex ion is anion, the name of the central metal atom is made

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to end in ‘ate’ followed by the oxd. no. in brackets.

B
C. For an acid we have a characteristic ending ‘ic’ eg H4[Pt(CN)6] is named
as hexacyanoplatinic (II) acid.

D. Naming of bridging groups in polynuclear coordination compaunds

If the complex contains two or more metal ions, it is called polynuclear. The
monodentate ligands that link the two metal atoms simultaneously are
called bridging ligands & are separated from the rest of the complex by
hyphens & denoted by the prefix  for eg.

(SO4)2

bis (ethylenediamine) cobalt (III) –  – anido –  – hydroxo bis

(ethylenediamine) cobalt (III) sulphate.

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The naming of some of the complexes is done as follows :- (as per IUPAC)
(1) K4[Fe(CN)6] potassiumhexacyanoferrate (II)
(2) K2[PtCl6) potassiumhexachloroplatinate (IV)
(3) [Co (NH3)6) Cl3 hexaminecobalt (III) chloride
(4) [Cr(H2O)4Cl4] CI tetraquadichlorochromium (III) chloride

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(5) [Pt(NH3)2CI4) diaminetetrachloroplatinum (IV)
(6) [Co(NH3)3 Cl3) triamminetrichlorocobalt (III)
(7) K3[Co(NO2)6 ] potassiumhexanitrocobaltate (III)

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(8) Na3[Fe(CN)5NO) sodiumpentacyanonitrosyl ferrate (II)
(9) [NiCI4]–2 tetrachloronickelate (II) ion

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(10) [Ru(NH3)5CI]+2 pentamminechlororuthenium (III) ion

in c
(11) When bidentate ligands are coordinated to the metal ion, their repitition is
indicated by pre fixes like bis, tris, tetrakis etc. for example :

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(1) [Fe(en)3] Cl3 trisethylenediamine iron (III) chloride
(2) [Ni (Gly)2] bisglycinatonickel (II)

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(12) If a complex ion has two metal atoms then it is termed polynuclear. The
ligand which connects . the two metal ions is called as Bridging Ligand or
Bridge group.

B
A prefix of Greek letter , is repeated before the name of each different kind
of bridging group.

tetraaqua iron(III)-hydroxo- - nitrotetraaquairon (III) sulphate.

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BONDING IN CO-ORDINATION COMPOUNDS
Following three theories are used to explain bonding in coordination compounds
(i) Werner’s Coordination Theory
(ii) Valence Bond Theory(VBT)
(iii) Crystal Field Theory(CFT)

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(i) Werner’s coordination theory
It’s postulates are :
(a) Metals possess two types of valencies called

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(i) primary or principle or ionizable valency.
(ii) secondary or non-ionizable valency.

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(i) Primary valency :- It refers to oxidation state of metal atom. for e.g. in

c
[Cu (NH3)4 ]+2 primary valency of Cu is + 2

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(ii) Secondary valency :- It refers to coordination no. of metal cation eg. in
[Co (NH3)6] Cl3 secondary valency of Co is 6.

P r
(b) Every metal atom has a tendency to satisfy both its primary & secondary
valencies. Primary valencies are satisfied by –ve ligands where as secondary
valencies are satisfied by –ve ions or neutral molecules (ligands)

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(c) The ligands satisfying secondary valencies are always directed towards fixed
positions in space thereby giving a definite geometry to the complex but the
primary valencies are non-directional.

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Experimental evidence to werner’s theory of complexes can be provided based on

(i) Precipitation of primary valencies on the addition of a suitable reagent.

e.g. - Fe(NH3)6Cl3 forms 3 moles of AgCl in the form of precipitate on addi-
tion of AgNO3 solution. This indicates that the complex ionises as
Fe(NH3)6Cl3 
2 
H O Fe(NH3)6+3 + 3CI–

(ii) Electrical conductance of complexes - More the number of ions provided

greater is the electrical conductance of the complex in aqueous medium.
e.g. - The electrical conductance of aqueous Fe(NH 3)6 Cl3 is greater than that
of aqueous solution of
[Fe(NH3)5CI] CI2. [Fe(NH3)5Cl]CI2 ® [Fe(NH3)5CI]+2 + 2Cl–
Total 3 ions Representation of complexes –

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Werner’s representation for Fe(NH3)6Cl3

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(Dotted lines indicate primary Valency and continuous lines indicate second-
ary valency of metal ion.)

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(a) If the complex is Fe(NH3)5Cl3 Then in this complex ‘Cl’ groups act as primary
valencies and one of the ‘Cl’ acts as secondary valency also. Thus werner’s
representation for this complex will be

c e
(b)

r in
Fe(NH3)4Cl3 In this complex ‘Cl’ groups act as primary valencies and two of
the ‘Cl’ group act as secondary valencies also. Thus this complex is represented

P
as

B y
Modern representation of complexes - Central metal ion along with second-
ary valencies or ligands are written in square brackets and primary valencies
outside the square bracket.
For example :- [Fe(NH3)6] CI3

Coordination sphere or inner sphere - This is written in square bracket. This

constitutes the central metal ion along with ligands. It is non-ionisable.

Outer sphere or lonisation sphere- This is written outside the square bracket.
In aqueous solution the groups written outside the square bracket dissociate
and are provided in the form of ions.
Limitations of Werner’s theory :-
(i) Only certain elements form coordination compounds & not others.
(ii) Why coordination sphere/entity possess definite geometry.
(iii) It does not explain how these compounds possess definite magnetic and
optical properties.
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Valence Bond Theory(VBT)

It’s postulates are

1. Each ligand is assumed to donate a pair of e–s to the central metal ion to
form a coordinate covalent metal ligand bond.

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2. The no. of metal ligand bonds which can be formed in the case of a given
metal ion depends upon the no. of vacant orbitals for bonding in metal ion
& is knwon as coordination no. of the metal ion.

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3. Orbitals of metal atom undergo hybridisation to give a set of hybrid orbitals
of equal energy.

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4. Sometimes, the unpaired (n – 1) d e–s pair up as fully as possible prior to

c
bond formation thus making some (n – 1) d orbitals vacant. The central
metal atom then makes available a no. of empty orbitals equal to its

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coordination no. for the formation of coordinate bonds with suitable ligand
orbitals.

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5. The hybridized metal orbitals are then allowed to overlap with those orbitals

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of ligands that can donate an e– pair for bonding. Each ligand has at least
one donor atom having ato least one sigma (s) orbital containing a lone
pair of e– s. As bond arises from the overlap of a vacant metal hybrid orbital

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& a filled orbital of the ligand.

6. Octahedral, square planar & tetrahedral complexes are formed as a result

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of d2sp3 (or sp3d2), dsp2 and sp3 hybridisation respectively.

This theory was mainly developed by linus Pauling. The main features of this
theory are
i. Every metal ion when it forms a complex compound undergoes formation
of coordinate covalent bond. During this bond formation the metal ion
acts as electron pair acceptor. For this the metal ion provides vacant
orbitals. The number of vacant orbitals provided is equal to the coordina-
tion number of metal ion.
For e.g. -In the formation of [Fe(NH3)6]3+ , Fe+3 ion provides six vacant
orbitals.
In [Cu(NH3)4]2+, Cu+2 ion provides four vacant orbitals.
ii. The metal provides vacant orbitals only after the process of hybridisation,
thus vacant hybrid orbitals are provided by the metal ion.
iii. The vacant hybrid orbitals of metal ion get overlapped by orbitals of
ligands containing lone pair of electrons.- The number of such overlappings
is equal to the coordination number of metal ion.
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iv. The empty ‘d’ orbitals involved in hybridisation may be inner (n-l)d or
outer “nd” orbitals. These complexes are called as Inner orbital complexes
and outer orbital complexes respectively.

v. If inner ‘d’ orbitals are involved in hybridisation, it is only through the

pairing of unpaired electrons in the ‘d’ orbitals of metal ion. Then such

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type of complexes will be diamagnetic or less paramagnetic and will be
called as Low spin complexes.

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this is not a postulate of VBT but we will use it here to understand
bonding easily.

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vi. In presence of strong field ligands pairing of electrons will occurr against

c
Pauli’s principle whereas in presence of weak field ligand no pairing will
take place. The order of ligands is

in
I– < Br– < S–2 < SCN– < Cl– < N3– < F– < OH– < C2O4–2 ~ H2O (weak field ligands)
< NCS– < H– < CN– < NH3 < en ~ SO3–2 < NO2– < Phen < CO (strong field

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ligands)
The order depends on the nature of donor atom i.e. its electronegativity

P
C-donor > N-donor >O-donor > halogen donor
vii. Generally all outer orbital complexes have paramagnetic nature and

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they are called as High spin complexes.

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Applications of valence Bond theory
OCTAHEDRAL COMPLEXES
* [Co(NH3)6]3+ .
* In the complex ion CO3+ ion is present

Co3+
3d 4s 4p 4d
As NH3 is a strong field ligand electrons get paired up the metal ion provides
vacant ‘3d’ orbitals for hybridisation.

Co+3 in [Co(NH3)6]3+ x x x x x x

3d 4s 4P
2 3
d sp hybridisation

* It is an octahedral complex.
* This is a diamagnetic complex. As inner ‘d’ orbitals are involved in hybridisation,
it is an inner orbital complex and it is a low spin complex.

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[CoF6]3–
In [CoF6]3– weak field ligand F is present so no pairing of electrons will ocurr
and the unpaired electrons remain as it is. Thus CO 3+ in [CoF6]3– will be

x x x x x x

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3d 4s 4p 4d
3 3
sp d hybridisation

* It is an octahedral complex.

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This is a paramagnetic complex. The outer ‘d’ orbitals are involved in
hybridisation, hence it is an outer orbital complex and a high spin complex.

c e
TETRAHEDRALCOMPLEXES

in
* [NiCl4]2–
Ni+2 ion has configuration of [Ar] 3d8

*
3d 4s

Thus Ni2+ in [NiCI4]2– will be

P r 4P

In this complex CI– is weak ligand, So the unpaired electrons remain as it is.

* B
3d

y x

4s
3
x

sp hybridisation
x x

4P

[NiCl4]2– has tetrahedral geometry due to sp 3 hybridisation and is para-

magnetic due to presence of unpaired electrons.
* [Ni(CN)4]2–
Ni 2+ in [Ni (CN)4]2–

x x x x
3d 4s 4P
2
dsp hybridisation

* CN– is strong ligand.Thus the unpaired electrons in ‘3d’ orbitals of Ni 2+ get

paired up.
* Thus the complex has square planar geometry. This Ni 2+ complex is an inner
orbital complex and a low spin complex and is diamagnetic.
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Shortcomings of VBT
1.It cannot explain why some complexes of metal ion in a particular oxd. state
are low spin ie inner orbital while some other complexes of the same metal
ion in the same oxd. state are high spin i.e. outer orbital complexes.

2. The mag. behaviour predicted by VBT is sometimes misleading for eg

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square planar complexes of Ni (II) should be diamagnetic but there are some
case in which Ni (11) is paramagnetic.

3. It does not give any satisfactory explanation for the colour of the

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complexes.

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4. It fails to explain the absorption spectra of coordination comkpounds.

in c
CRYSTAL FIELD THEORY(CFT)
Above short comings has been explained by CFT (Crystal field thoery)

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It’s postalates are as follows :-

1. Where as valence bond thoery considers the metal ligand bond to be

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covalent, CFT considers the bond to be ionic arising purely from electrostatic
interactions between similar to those between the ions in a crystal, that is
why it has been named as crystal field thoery (CFT).

2.

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It treats ligand as a point of –ve charge & their arrangements around

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the central metal ion is such that the
points (ligands) are min.

3.
repulsions between these – ve

The five d-orbitals can be divided into two groups depending upon the
nature of their orientation in space -

A. The three d-orbitals (dxy, dyz, dzx) which orient in the regions in between
the co-ordinate axes are designated as t2g orbitals.
B. The two other orbitals d x 2  y 2 & d z 2 which orient along the axes are labelled
as eg orbitals.

In the case of a free ion or in a isolated gaseous metal atom/ion all the five
d-orbitals have the same energy i.e. they are degenerate meaning energetically
alike.
But when the ligand approaches the central metal ion, the e– s in d-
orbital of the central metal ion will be repelled by the lone pairs of the
ligands. As a result of these interactions, the degeneracy of d-orbitals of the
metal ion is lost & these split into two set of orbitals having different energies.

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This is known as Crystal field spliting .

Crystal field splitting in tetrahedral complexes

In tetrahedral complexes the three d-orbitals dxy, dyz & dxz are pointing
close to the direction in which ligands are approaching. As a result of this, the
energy of these three orbitals increases much more than the other two

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d-orbitals d x 2  y 2 & d z 2 . The d-orbitals will thus split as shown below :-

e S
in c
t Crystal field spiliting energy in tetrahedral field

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Crystal field splitting in octahedral complexes
In octahedral complexes, the two d-orbitals lying along the axis namely

P
d x 2  y 2 & d z 2 will suffer more electrostatic repulsions as ligands are approaching

the central metal atom along the axis & hence their energy will be greater
than the other three d-orbitals (dxy, dyz, dzx) accordingly, the d-orbitals will

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thus split as follows :- Fig.

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0 Crystal field spiliting energy in octahedral field

Note  0 is greater than t as more number of ligands are present (i.e.6)

in octahedral complexes as compared to tetrahedral complex.
4
t = 
9 O

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Filling of electrons in orbitals
Pairing energy - The energy required to pair up two electrons is called pairing
energy.

If D0 is less than P (D0 < P) we have the so called weak field, high spin situation
& the fourth e– enters one of the eg orbitals giving the configuration t32g

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eg1. If now fifth e– is added to a weak field coordination entity, the
configuration becomes t32g eg2.

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When D0 > P, we have the strong field, low spin situation and pairing will
occur in the t2g leavel with the eg. level remaining occupied in evtities of d 1
to d6 ions.

c e
¶ It has been found that coordination entities with four to seven d e– s are more
stable for strong field as compared to weak field cases.

r in
Factors affecting crystal field splitting ()

1. Nature of the metal ion :- For metal atoms belonging to same subgroup as the value

P
of  increases the magnitude of  decreases. It ­ses by 30% to 50% from 3d
to 4d series.

y
2. Oxidation state of metal ion :- Higher is the oxd. state of the metal ion larger is the
value of D (CFSE). This is bcoz the central metal ion with higher oxd. state
polarises the ligand more effectively. As a result the ligand approaches the

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central atom more closely & hence a greater splitting or CFSE is observed.

3. Nature of ligand :-
A stronger ligand has higher splitting power than a weak ligand. The common
ligands arranged in the order of ­sing splitting power are given below. It is
called spetrachemical series.
I < Br– < S–2 < SCN– < Cl– < N3– < F– < OH– < C2O4–2 ~ H2O (weak field ligands)
–

< NCS– < H– < CN– < NH3 < en ~ SO3–2 < NO2– < Phen < CO (strong field ligands)

4. Geometry of the complex :-

The value of t (CFSE of tetrahedral complex) is 50% as large as that of 0
(CFSEof octahedral complex)

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Colour of complex ions
Intra d-d transitions accounts for the colour of complex ions & their
compounds the absorption of electromagnetic rediations by an ionic species in
sol. requires that e–s within the ion undergo a transition from one energy
state to another. To cause this transition a suitable wavelength component is
absorbed and the transimitted light corresponds to a particular colour.

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The colour of a particular compound depends upon the magnitude of ,
the crystal field splitling which in turn depends upon the nature of ligand.

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Magnetic properties
Transition metal complexes are known to be paramagnetic in character. The

e
magnetic properties of a substance depend upon the oxd. state, electronic
config. coordn no. of central metal & the nature of ligand field.

c
Magnetic moment is expressed as :

in
eh
B 
e  charge on e–4, mc

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m  mass of e–,
h  plank’s constant,

P
c  vel. of light.

Thus value of  B = 9.274 × 10–21 ergs gauss–1.

y
This is taken as aunit of magnetic moment called bohr magnetom(B.M.)

Paramagnetic substances :- A substance containing one or more unpaired e–s has

B
a definite value of magnetic moment & is attracted in external magnetic
field.

Diamagnetic substance :- Substances having paired e–s will have zero magnetic
moment & hence do not possess magnetic propertics.

Magnetic moment of a substance depends up on the no. of unpaired e– s ie.

greater is the no. of unpaired e– s, more is the magnetic moment.
Thus we have magnetic moment,
u = n(n + 2) B.M. ( Bohr Magnetons )

Thus from the knowledge of no. of unpaired e–s & the value of magnetic
moment (), we can find :-
A. Valence state of the metal ion in a given complex

B. Nature of bonding in the complex ie. spin free or spin paired type.
Stability of coordination compounds in sol.

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1. The formation of coordination compound involves reaction between a
metal ion & ligands. If the force of attraction of the metal ion with ligend is
strong a stable complex may result.

2. Though the complex ions are highly stable, their possibility of dissociation
in aqueous sol’s cannot be neglected though these may be dissociated to a

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small extent.

3. Thus a chemical equilibrium may be established between the undissociated

complex & the dissociated ions.

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(MLn)b+ Ma+ + nLx–
Where b+ , a+, x– are respective charges on the complex, Metal atom &

e
ligand respectively.
Thus the equilibrium constant of above reaction may be given as :-

c
[M a + ][Lx ]n

in
K =
[MLn b + ]

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The reciprocal of the above constant K, is called stability constant (K s).

Greater the value of Ks more is the stability of the complex

constant (Kn) for eg.

P
The stability of any complex can also be expressed in terms of its formation

y
[M(H2O)n] + nL [MLn] + nH2O

B
Step I  M+L ML
[ ML ]
The formation constant for this step K1 =
[ M ][ L ]
Step II  ML + L ML2
[ ML 2 ]
The formation constant for this step K 2 =
[ ML ][ L ]
Similarly for nth step  MLn-1 + L [MLn]
[ MLn ]
Kn =
[ MLn 1 ][L ]
For over all reaction  Ks = K1 × K2 × K3 .......... Kn.

Here K1, K2, K3 ....... etc are stepwise formation constants or stepwise
stability constants while Ks is termed as overall formation constant

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Factors affecting the stability of complex
1. Nature of central metal ion :-
Nature means the charge density on central ion ie greater is the charge
density or larger the charge /
radius ratio, more is stability of a complex for eg.

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Fe+3 + 6CN– [Fe(CN)6]–3 ; K = 1.2 ×
31
10
Fe+2 + 6CN– [Fe(CN)6]–4 ; K = 1.8 ×

S
6
10 .
Thus out of two complexes, these of Fe+3 are more stable.

e
Greater the charge density on the metal ion. greater the metal ion will have

c
tendency to form the complex. Thus the complexes formed by metal ion with
high charge density are more stable than complexes formed by metal ion with

in
less charge density. For e.g. - Fe+3 ion forms a more stable complex than Fe+2,
Similarly Pt2+ complex is more stable than Pt2+ complex.

r
The stability of the complexes of some of the cations having same charge but
different ionic radii decrease with the increase in ionic radii.

P
Ion Cu+2 > Ni+2 > CO+2 > Fe+2 > Mn2+
Ionic radii 0.69 0.78 0.82 0.83 0.91

y
2. Nature of ligand :-
A. Basic character of ligands :-

B
More basic is a ligand, greater is the ease with cohich it can donate its
e– s & therefore more is the stability of the complex for eg complexes in
volving F– are more stable than those involving Cl – ions or Br– ions.
(Weak acid  strong conjugate base
Acid character HF < HCl < HBr
Conjugate basic charater F– > Cl– > Br–

B. Charge on ligands :- Higher the charge & smaller their size, the more stable
are the complexes.
C. Chelate Effect :- Complexes containing cheloate rings are usually more
stable than similar complexes containing no rings called as chelate effect.
For e.g. Ni+2 (aq) + 6NH3 (aq) [Ni(NH3)6]+2(aq.) log K = 7.99

Ni+2 (aq) + 3en (aq) [Ni(en)3]+2(aq) log K = 18.1

3. Class a & class b metals :- Chatt & Ahrland have classified the metals into two categories i.e.
a, b

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 Reconstruct Your Chemistry With Prince Sir
A.Class a metals :- H, group 1 (alkali metals), group 2 (alkaline earths), the elements
Sc to Cr, Zn to Br, In, Sb, Sn. These metals form stable complexes with ligands
containing N, O & F groups.

B.Class b metals :- Rh, Pd, Ag, Ir, Pt, Ar, Hg. These elements have fully filled

ri
d-orbitals & therefore form more stable complexes with ligands whose donor
atoms are heavier member of N, O & Fgroups.

Isomerism in coordination compound

e S
c
Two or more substances having the same molecular formula but different

in
structural or spatial arrangement are called isobers & the phenomenon is
called isomerism. It is of two types :-

r
A. Structural isomerism B. Stereo isomerism

P
A.Structural isomerism :- It arises due to the difference in structures of coordination
compounds. It may be classified as follows

y
1.Ionisation isomerism
Compounds which give different ions in solution atthough they have

B
same composition are called ionization isomers. eg.
[Co (NO3) (NH3)5]SO4 & [Co(SO4) (NH3)5] (NO3)

2.Hydrate isomerism
Compounds having same composition but differ in the no. of water molecules
present as ligands (i.e. in coordination sphere) & as molecules of hydration
(outside coordination sphere) are called hydrate isomers. for eg.

[Cr(H2O)6]Cl3 , [CrCl(H2O)5]Cl2 ×H2O, [CrCl2CH2O)4]Cl × 2H2O

These complexes differ from one another with respect to the number of water
molecules acting as ligands. They also differ in their number of primary
valencies i.e., chloride ions which are provided. Other hydrate isomers are
[Co(NH3)4 H2O CI] Cl2 [Co(NH)4 Cl2] Cl. H2O

3.Linkage isomerism
Isomerism of this type ocurs when more than one atom in a momodentate
ligand may function as a donor for eg.
[Co(ONO) (NH3)5]+ 2 [Co(NO2) (NH3)5]+ 2

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 Reconstruct Your Chemistry With Prince Sir
4.Coordination isomerism
This type of isomerism is possible when both + ve & – ve ions of a salt are
complex ions & the two isomers differ in teh distribution of ligands in the
cation & anion for eg.

[Co(en)3] [Cr(CN)6] & [Cr(en)3] [Co(CN)6]

ri
This type of isomerism is exhibited when the complex has two complex ions
in it ‘Cationic and anionic’. This type of isomerism is caused by the inter-
change of ligands and metal ions between the two complex ions of the same

S
complex
(i) [Co(NH3)6] [Cr(CN)6] (ii) [Co(NH3)6] [Cr(C2O4)3]

e
[Cr(NH3)6] [Co(CN)6] [Cr(NH3)6] [Co (C2O4)3]

in c
Stereo isomerism or space isomerism

It is exhibited by isomers having the same structure but differ in their

r
spatial arrangements ie having different configurations. It is of two types :-
A. Geometrical isomerism B. Optical isomerism

P
A.Geometrical isomerism
In metal complexes the ligands may occupy different types of positions around

y
the central metal atom. These positions may either next to one another (cis) or
opposite to each other (trans).Hence it is also called as trans isomerism.

B
 It is not shown by the complexes having coordination no’s 2 & 3, it has also
not found in tetrahedral complexes.
 Tetrahedral geometry does not show geometrical isomerism because each
position is adjacent to one another.

 It occurs in square planar (4-coordinate) & octahedral (6-coordinate)

complexes.

(i) Square planar complexes

The planar complexes of the type Ma 2b2 can exist in is or trans forms.

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 Reconstruct Your Chemistry With Prince Sir
(ii) Octahedral complexes
1. Ma4b2 complexes
In this class of complexes eg [M(NH3)4Cl2] two geometrical isomerism, one
cis & the other trans, are possible.
+ +

ri
S
cis - dichlorotetrammine metal (III) ion trans - dichlorotetrammine metal (III) ion

c e
2. Ma3b3 complexes
In this type of isomerism, if each trio of donoor atoms (similar groups) occupy

in
the corners of one of the octahedral faces & hence is called facial or
face-isomer (cis form) while in trans form the positions of trio of doner atoms
are around the meridian of the octahedron. Hence it is called meridional or

r
mor-isomer .

y P
B Geometrical or cis-Trans isomer
The ligands occupy different positions around the central metal ion. When
two identical ligands are coordinated to the metal ion from same side then
it is cis isomer. (in Latin, cis means same). If the two identical ligands are co
ordinated to the metal ion from opposite side then it is Trans isomer (in
Latin, Trans means across). These geometrical isomers differ in physical as
well as chemical properties.

* Geometrical isomerism is most important in compounds with coordination

numbers 4 and 6. 4-coordinated complexes with tetrahedral geometry do
not exhibit - cis- Trans isomerism.

* It is exhibited by 4-coordinated complexes with square planar geometry.

* Ma2b2, Ma2bc type of square plannar complexes exhibit geometrical

isomerism and gives two gometrical isomers each.
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 Reconstruct Your Chemistry With Prince Sir
Mabcd (Square planar) gives three isomers.
e.g. [Pt(NH3)2Cl2]

ri
e S
in c
P r
*

Mabcdef
Ma2b2c2
Ma2bcd
B y
Other 6-Coordinated geometrical isomers are
General formula Total No. of geometrical isomers
15
5
4
Ma4b2 2
Ma4bc 2
Ma3b3 2
Ma6, Ma5b Nil Here M = central atom a, b, c, d, e, f = ligands

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 Reconstruct Your Chemistry With Prince Sir
Optical isomerism
Optical isomers rotate the plane of polarised light in opposite directions the
two isomers are structurally non-superimposable mirror image of each other.
The optical isomers are called dextro and laevo (d & l) depending upon the
direction in which plane of the polarised light is rotated.

ri
The d & l isomers of a compound are called exantiomers. When the
rotation is to the left, the isomer is called laevorotatory (l or –) & when
the rotation is to the right the isomer is called as dixtrorotatory (d or +). A

S
1 : 1 equilibrium mix. of the d & l isomers gives a racemic mixture with a net
zero rotation.

c e
1. [M(aa)3] type
i.e. containing three symmetrical bidentate ligand eg [Co(en)3]+3 & [Cr (ox)3]–

in
3

P r
y
2. [M(aa)2b2] or [M(aa)2bc] type
i.e. containing two symmetrical bidentate ligands eg [CoCl2(en)2]+. However
in this type, cis isomer shows optical isomerism as it is unsymetrical but tran

B
isomer does not show optical isomerism since it is symmetrical for eg.

-2

* Optically active complexes are those which are nonsuperimposable over the
mirror image structure. An optically active complex is one which is asymmet-
ric in nature i.e., not divisible into two identical halves.
* The complex which rotates plane polarised light to left hand side is laevo
rotatory i.e. ‘l’’ or ‘-’ and if the complex rotates the plane polarised light to
right hand side then it is dextro rotatory ‘d’ or ‘+’
* Thus complexes which have same physical and chemical properties but differ
in their action towards plane polarised light are called as optical isomers.

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 Reconstruct Your Chemistry With Prince Sir
* The ‘d’ and ‘t’ isomers of a compound are called as Enantiomers or Enantio-
morphs. 4-coordinated complexes with tetrahedral geometry exhibit optical
activity
* Only those 6-coordinated complexes in which there are chelating agents i.e.
bidentate ligands, exhibit optical isomerism For e.g.

ri
[Fe(NH3)2(en)Cl2]–

e S
in c
*

P r
Trans - [Fe(en)2Cl2] do not show optical activity due to superimposition of
their mirror image.

e.g
B y
ORGANOMETALLIC COMPOUNDS OR C - METAL BOND COMPOUNDS
Introduction
Definitiaon - Compounds containing one or more metal carbon bonds.
The compounds of metalloids (Ge, Sb) and non metals (B, Si, P, As etc.) which
are less electro -ve than carbon are also categorised in this title.
R - Zn - R dialkyl zinc (Frankland reagent)
R - Mg - X Alkyl Mg halide (Grignards reagent)
* Compounds like

Sodium acetati CH3 –COONa

Sodium ethoxide C2H5 –O–Na
Sodium Mercaplide H3C–SNa are not organometallic compd. as
In these compounds metal is not directly attached with carbon atom.
H3CO
B(OCH3)3 is not OMC  B-OCH3
H3CO

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 Reconstruct Your Chemistry With Prince Sir
OCH3
while CH3B(OCH3)2 is OMC ® H3C - B
. OCH3
* Cyanides. carbides and carbonates are not considered OMC because in these
compds metal is not attached to carbon of alkyl gp. or carbon of carbonyl gp.

Classification of Organometallic Compounds

OMC can be classified into three main categories

ri
S
(a)  - bonded OMC :
These compounds are fomed mostly by non transition and metalloid

e
elements.

c
eg. R - Mg - X, (grignard’s reagent)

in
(CH3)2Zn (Dimethyl zinc or frankland’s reagent)
(R)2Cd, (dialkyl cadmium)

r
(C2H5)4Pb (Tetra ethyl lead)
(CH3)3Al, TiCl4 (Ziegler natta catalyst) etc.

(b)

eg.
 - bonded OMC :

y P
These are usaully formed by transition metals.
Ferrocene [Fe(n5 - C5H5)2]

B
where n = No. of carbon atoms combined with metal atom.
Zeise’s salt K[PtCI3(h2 - C2H4)]
Dibenzene chromium [Cr(n6 - C6H6)2]

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 Reconstruct Your Chemistry With Prince Sir
(e)  and  - bonded OMC :
Transition metals of gp. 6, 7,8,9 and 10 in their zero oxidation state form
such type of OMC.
The carbonyl compds. of these metals have both s, and p bonds. e.g.
[Ni(CO)4], [Fe(CO)5], [Mn2(CO)8] , [M(CO)6] where M is Cr, Mo, W.

ri
The metal-carbon bond in metal carbonyls possess both s-and p-bond character.
Transition metals give carbonyls which are volatile and posses diamagnetic

S
character. Some typical metal carbonyls are
CO CO CO

e
CO OC CO
Ni Fe M

c
OC CO OC CO OC CO

in
CO CO CO
Ni (CO)4 Fe(CO)5 M=Cr or Mo in M(CO)6

r
Application of Organometallic Compounds

P
(1) As homogeneous Catalyst

B y
(2) As heterogenous catalyst

Zeigler – Natta Catalyst

Tri alkyl AI ¬Titanium tetrachloride used for)– Polymerisation

(3) Organic synthesis - OMC like R - Mg - X, R2 - Cd, CH3 - Li etc. are used for preparation of almost
all type of organic compds. .
(4) As petrol additive - TEL(Tetraethyl lead) is used as antiknock compd. in petrol.
(5) In medicine - Organo arsenic compds are used as medicine for syphilis deases.
(6) In agricuture - Seeds are treated with ethyl Hg Chloride to protect the plants against infection.

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 Reconstruct Your Chemistry With Prince Sir
JEE MAINS
Q.1 The magnitude of crystal field stabilisation energy in octahedral field depends on
I : the nature of the ligand
II : the charge on the metal ion
III : whether the metal is in the first, second or third row of the transition elements.
(A) I, II, III only correct. (B) I, II only correct

ri
(C) II, III only correct (D) III only correct

Q.2 Tetrahedral complexes are formed

S
I: where the central metal has a low oxidation state
II : where ligands are weak field
III : where the electronic configuration of the central metal is , d0, d5 or d10

e
(A) I, II, III only correct (B) I, II only correct

c
(C) II, III only correct (D) III only correct

in
Q.3 Which of the following ligands is called -acceptors ?
CO CN – NO+

r
(I) (II) (III)
(A) I, II, III only correct. (B) I, II only correct
(C) II, III only correct (D) III only correct

P
Q.4 Coordination compounds [Pt(NH3)3(NCS)] and [Pt(NH3)3(SCN)] are examples of ..............isomerism
(A) coordination (B) linkage

y
(C) ionizaiton (D) optical
Q.5 The correct name of, [Ni(DMG)2] a cherry red precipitate is

B
(A) bis (dimethyl glyoximato) nickel (II) (B) bis (dimethyl glyoximato) nickelate (II)
(C) bis (dimethyl glyoxime) nickel (II) (D) bis (dimethyl glyoxime) nickelate (II)
Q.6 A solution containing 0.319 g of CrCl3.6H2O was passed through a cation exchange resin in the acid
form, and the acid liberated was titrated with a standard solution of NaOH. This required 28.5 cm3 of
0.125 M NaOH. The correct formula of the Cr (III) complex is
(A) [Cr(H2O)6]Cl3 (B) [CrCl(H2O)5]Cl2.H2O
(C) [CrCl2(H2O)5]Cl.2H2O (D) [CrCl3.(H2O)3].3H2O
Q.7 In which of the following pairs both the complexes show optical isomerism ?
(A) cis-[Cr(C2O4)2Cl2]3–, trans-[Co(NH3)4Cl2]
(B) [Co(en)3]Cl3, cis-[Co(en)2Cl2]Cl
(C) [PtCl (dien)]Cl, [NiCl2Br2]2–
(D) [Co(NO3)3 (NH3)3], cis-[Pt(en)2Cl2]
Q.8 In Fe(CO)5 , the Fe–C bond possesses :
(A)  character only (B)  character only (C) ionic character only (D) both  and  characters
Q.9 [Cr(H2O)6]Cl3 (atomic number of Cr = 24) has a magnetic moment of 3.83 B.M. The correct distribution
of 3d electrons in the chromium present in the complex is:
(A) 3d1xy, 3d1yz, 3d1zx (B) 3d1xy, 3d1yz, 3d1z2
(C) 3d1( x 2  y 2 ) , 3d1z 2 , 3d1xz (D) 3d1xy , 3d1( x 2  y 2 ) , 3d1yz

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 Reconstruct Your Chemistry With Prince Sir
Q.10 Which of the following statements is INCORRECT ?
(A) The stability constant of [Co(NH3)6]3+ is greater than that of [Co(NH3)6]2+.
(B) The cyano complexes are far more stable than those formed by halide ions.
(C) The stability of halide complexes follows the order I < Br < Cl.
(D) The stability constant of [Cu(NH3)4]2+ is greater than that of [Cu(en)2]2+

ri
Q.11 The IUPAC name of the Wilkinson's catalyst [Rh Cl (P Ph3)3] is
(A) Chloridotris (triphenylphosphine)rhodium (I)
(B) Chloridotris (triphenylphosphine)rhodium (IV)
(C) Chloridotris (triphenylphosphine)rhodium (0)

S
(D) Chloridotris (triphenylphosphine)rhodium (VI)

For which of the following types of dn configuration, the number of unpaired electrons in octahedral

e
Q.12
complexes remains same irrespective of the ligand field strength.

c
(A) d3 (B) d4 (C) d5 (D) d6

in
Q.13 The complex ion which has no 'd' electrons in the central metal atom is
(A) [MnO4]– (B) [Co(NH3)6]3+

r
(C) [Fe(CN)6] 3– (D) [Cr(H2O)6]3+

P
Q.14 The spin magnetic moment of cobalt in the compound K2[Co(SCN)4] is
(A) 3 BM (B) 8 BM

y
(C) 15 BM (D) 24 BM

Q.15 The formula of a complex with composition CrCl3.6H2O giving the following observations:

B
Number of ions = 3 ; Number of Cl– ions = 2 ; Number of non-ionic Cl = 1 is
(A) [Cr (H2O)6]Cl3 (B) [CrCl (H2O)5]Cl2.H2O
(C) [CrCl2(H2O)4]Cl.2H2O (D) [CrCl3(H2O)3].3H2O

Q.16 If 1.00 mol of each of the following compounds is dissolved in water, which one will produced maximum
number of ions ? Assume that dissociation is complete.
(A) [Cu(NH3)4]SO4.H2O (B) K4[Fe(CN)6]
(C) [Cr(H2O)6](NO3)3 (D) K[PtCl3(C2H4)]

Q.17 The formula for the compound tris (ethane-1, 2-diamine)cobalt (III) sulphate is
(A) [Co(en)3]SO4 (B) [Co(SO)4(en)3]
(C) [Co(en)3](SO4)2 (D) [Co(en)3]2(SO4)3

Q.18 Which of the follwoing electronic arrangement gives the highest value of the magnetic moment?
(A) d6, strong field (B) d7, high spin
4
(C) d , weak field (D) d2, strong field

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 Reconstruct Your Chemistry With Prince Sir
Q.19 Which of the following is correctly matched ?
Column I Column II Column III
(A) [Cr(CO)6] Paramagnetic Octahedral, sp3d2
(B) [Fe(CO)5] Paramagnetic Trigonal bipyramid, sp3d
(C) [Co(CO)4]– diamagnetic tetrahedral, sp3
(D) [Ni(CO)4] diamagnetic spuare planar, dsp2

ri
Q.20 In which of the following metal carbonyls the C – O bond order is lowest?
(A) [V(CO)6]– (B) [Mn(CO)6]+ (C) [Cr(CO)6] (D*) [Ti(CO)6]2–

S
Q.21 Which of the following names is/are correct for the compound Na[CoCl2(NO2)(-C3H5) (NH3)2]
(A) Sodium allyldiamminedichloridonitritocobaltate (III)
(B) Sodium diamminedichloridoallylnitrito-N-cobaltate (III)

e
(C*) Sodium diamminedichloridocyclopropylnitrito-N-cobaltate (III)

c
(D) Sodium diamminecyclopropylnitrito-N-dichloridocobaltate (III)

in
Q.22 Which is not the possible IUPAC name(s) of coordination positional isomer(s) of complex ion

r
2+
OH
Cl3(NH3) Pt Pt(NH3)3Cl is/are

P
OH
(A) Di--hydroxido bis {diamminedichloridoplatinum (IV)} ion
(B) Bis{-hydroxidodiamminedichloridoplatinate (IV)} ion

y
(C) Tetrachloridoplatinum (IV) di--hydroxidotetraammineplatinum (IV) ion
(D) Diamminedichloridoplatinum (IV) di--hydroxidodiamminedichloridoplatinum (IV) ion

B
Q.23 Arrange the following compound according to dC–C order.
(I) C2F4 (II) C 2H 4 (III) [PtCl3(C2H4)]¯
(A) I > II > III (B) III > II > I (C) II > I > III (D) II > III > I

Q.24 Statement-1 : In Zeise's salt C – C bond order regarding ethylene molecule is less than two.
Statement-2 : Ethylene accepts electron pair from filled d-orbital of Pt2+ into its vacant bonding
M.O.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

Q.25 Statement-1 : [V(CO)6] can not act as oxidising agent.

Statement-2 : It can not be reduced by reducing agent.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is false.
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 Reconstruct Your Chemistry With Prince Sir
Q.26 The hybrisation involved in [CoF6]3– is:
(A) d2sp3 (B) d3sp2 (C) dsp3 (D) sp3d2

Q.27 Which of the following is  complex:

(A) Trimethyl aluminium (B) Ferrocene
(C) Diethyl zinc (D) Nickel carbonyl

ri
Q.28 Which complex is likely to show optical activity:
(A) Trans-[CoCl2(NH3)4]+ (B) [Cr(H2O)6]3+
(C) Cis-[Co(NH3)2(en)2]3+ (D) Trans-[Co(NH3)2(en)2]3+

S
Q.29 Which one is the most likely structure of CrCl3·6H2O if 1/3 of total chlorine of the compound is precipitated

e
by adding AgNO3 to its aqueous solution:
(A) CrCl3·6H2O (B) [CrCl3(H2O)3]·(H2O)3

c
(C) [CrCl2(H2O)4]·Cl·2H2O (D) [CrCl(H2O)5]Cl2 ·H2O

in
Q.30 The two compounds [Co (SO 4 )( NH 3 ) 5 ]Br and [Co (SO 4 )( NH 3 ) 5 ]Cl represent:

r
(A) Linkage isomerism (B) Ionisation isomerism
(C) Co-ordination isomerism (D) No isomerism

P
Q.31 The structure of iron pentacarbonyl is:
(A) Square planar (B) Trigonal bipyramid
(C) Triangular (D) None of these

y
Q.32 The EAN of platinum in potassium hexachloroplatinate (IV) is:

B
(A) 46 (B) 86 (C) 36 (D) 84

Q.33 Diethylene triamine is:

(A) Chelating agent (B) Polydentate ligand
(C) Tridentate ligand (D) All of these

Q.34 How many moles of AgCl would be obtained, when 100 ml of 0.1 M CoCl3(NH3)5 is treated with
excess of AgNO3?
(A) 0.01 (B) 0.02 (C) 0.03 (D) none of these

Q.35 0.001 mol of Co(NH3)5(NO3)(SO4) was passed through a cation exchanger and the acid coming out of
it required 20 ml of 0.1 M NaOH for neutralisation. Hence, the complex is
(A) [CoSO4(NH3)5]NO3 (B) [CoNO3(NH3)5]SO4
(C) [Co(NH3)5]SO4NO3 (D) none of these

Q.36 Which of the following has five donor (coordinating) sites?

(A) Triethylene tetramine (B) Ethylenediamine tetracetate ion
(C) Ethylenediamine triacetate ion (D) Diethylene triamine

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 Reconstruct Your Chemistry With Prince Sir
Q.37 In the compound CoCl3·5NH3
(A) all the Cl show primary valency (PV) only
(B) two Cl show (PV) and one Cl secondary valency (SV)
(C) two Cl show (PV) and one Cl (PV) as well as (SV)
(D) all the Cl show (SV)

ri
Q.38 The two compounds pentaamminesulphatocobalt(III) bromide and
pentaamminesulphatocobalt(III) chloride represent
(A) Linkage isomerism (B) Ionization isomerism
(C) Coordination isomerism (D) No isomerism

S
Q.39 Which of the following is an oxidizing agent?

e
(A) Mn(CO)5 (B) Fe(CO)5 (C) Mn2(CO)10 (D) Fe2(CO)9

c
Q.40 EAN of the elements (*) are equal in:

in
* * * *
(A) N i (CO)4, [ Fe (CN)6]4– (B) [ N i (en)2]2+, [ Fe (H2O)6]2+
* * * *
(C) [ Co (CN)6]3–, [ Fe (CN)6]3– (D) [ N i (en)2]2+, [ Sc (H2O)6]3+

r
Q.41 Which of the following statements is incorrect?

P
(A) Co-ordination compounds and complexes are synonymous terms.
(B) Complexes must give ions in the solution.
(C) Complexes may give ions in the solution or may not give ions in the solution.

y
(D) Generally complex ion does not dissociate into its component parts even in the solution.

Q.42 Which one of the following is an example of coordination isomerism?

B
(A) [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br
(B) [Co(NH3)5NO2]Cl2 and [Co(NH3)5ONO]Cl2
(C) [Cr(H2O)6]Cl3 and [Cr(H2O)5Cl]Cl2 ·H2O
(D) [Cr(NH3)6][Co(CN)6] and [Co(NH3)6][Cr(CN)6]

Q.43 Select correct code about complex [Cr(NO2)(NH3)5][ZnCl4]

(I) IUPAC name of the compound is Pentaamminenitrito-N-chromium (III) tetrachloridozincate (II)
(II) It shows geometrical isomerism
(III) It shows linkage isomerism
(IV) It shows co-ordination isomerism
(A) III, IV (B) I, III & IV (C) II, III & IV (D) I, II, III & IV

Q.44. Consider the following complexes:

(I) K2PtCl6 (II) PtCl4· 2NH3 (III) PtCl4· 3NH3 (IV) PtCl4·5NH3
Their electrical conductances in an aqueous solutions are:
(A) 256, 0, 97, 404 (B) 404, 0, 97, 256 (C) 256, 97, 0, 404 (D) 404, 97, 256, 0

Q.45. Which of the following complexes can exist as diastereoisomers?

(A) [Cr(NH3)2Cl4]– (B) [Co(NH3)5Br] 2+
(C) [FeCl2(NCS)2]2– (D) [PtCl3Br]2–

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 Reconstruct Your Chemistry With Prince Sir

Q.46. Lead poisoning in the body can be removed by: [3]

(A) EDTA in the form of calcium dihydrogen salt
(B) cis-platin
(C) Zeisse’s salt
(D) DMG

ri
Q.47. How many geometrical isomers are possible for [Pd2+ (NH2–CH(CH3)– CO 2 )2]o [3]
(A) 2 (B) 3 (C) 4 (D) 6

S
Q.48. Isomerisms exhibited by [Cr(NH3)2(H2O)2Cl2]+ are [3]
(A) ionisation, optical (B) hydrate, optical

e
(C) geometrical, optical (D) coordinate, geometrical

c
Q.49 Of the following complex ions, one exhibits isomerism. That is: [3]

in
(A) [Ag(NH3)2]+ (B) [Co(NH3)5NO2]2+
(C) [Pt(en)Cl2] (D) [Co(NH3)5Cl]2+

r
Q.50 [Cr(NH3)5Br]Cl and [Cr(NH3)5Cl]Br can be distinguished by/and isomerism shown is: [3]
(A) BaCl2, ionisation (B) AgNO3, ionisation

P
(C) AgNO3, coordinate (D) BaCl2, linkage

Q.51 If excess of AgNO3 solution is added to 100 mL of a 0.024 M solution of dichlorobis (ethylene diamine)

y
cobalt (III) chloride, how many mol of AgCl be precipitated: [3]
(A) 0.0012 (B) 0.0016 (C) 0.0024 (D) 0.0048

B
Q.52 Which kind of isomerism is exhibited by [Co(EDTA)]— [3]
(A) Optical & geometrical isomerism (B) Geometrical isomerism
(C) Optical isomerism (D) No isomerism
Q.53 The EAN of metal atoms in Fe(CO)2(NO)2 and Co2(CO)8 respectively are
(A) 34, 35 (B) 34, 36 (C) 36, 36 (D) 36, 35

Q.54 Following Sidgwick's rule of EAN, Co(CO)x will be

(A) Co2(CO)4 (B) Co2(CO)3 (C) Co2(CO)8 (D) CO2(CO)10

Q.55 On treatment of [Ni(NH3)4]2+ with concentrated HCl, two compounds I and II having the same formula,
[NiCl2(NH3)2] are obtained, I can be converted into II by boiling with dilute HCl. A solution of I reacts
with oxalic acid to form [Ni(C2O4)(NH3)2] wheras II does not react. Point out the correct statement of
the following
(A) I cis, II trans; both tetrahedral (B) I cis, II trans; both square planar
(C) I trans, II cis; both tetrahedral (D) I trans, II cis; both square planar

Q.56 Which one of the following statement is incorrect ?

(A) Greater the formation constant (Kf) of a complex ion, greater is its stability.
(B) Greater the positive charge on the central metal ion, greater is the stability of the complex

33
 Reconstruct Your Chemistry With Prince Sir
(C) Greater is the basic character of the ligand, lesser is the stability of the complex.
(D) Chelate complexes have high stability constants.
Q.57 Point out the correct statements amongst the following
(A) [Cu(CN)4]3– has tetrahedral geometry and dsp2 hybridization
(B) [Ni(CN)6]4– is octahedral and Ni has d2sp3 hybridization

ri
(C) [ZnBr4]2– is tetrahedral and diamagnetic
(D) [Cr(NH3)6]3+ has octahedral geometry and sp3d2 hybridization

Q.58 Among the following ions which one has the highest paramagnetism

S
(A) [Cr (H 2O) 6 ]3 (B) [Fe(H 2O) 6 ]2 (C) [Cu(H2O)6]2+ (D) [Zn((H2O)6]2+

e
Q.59 Among the following, the compound that is both paramagnetic and coloured is
(A) K2Cr2O7 (B) (NH4)2[TiCl6] (C) VOSO4 (D) K3[Cu(CN)4]

in c
Q.60 In the isoelectronic series of metal carbonyl, the CO bond strength is expected to increase in the order.
(A) [Mn(CO) 6 ] < [Cr(CO)6] < [V(CO)6]–

r
(B) [V(CO)6]– < [Cr(CO)6] < [Mn(CO) 6 ]
(C) [V(CO)6]– < [Mn(CO)6]+ < [Cr(CO)6]

P
(D) [Cr (CO) 6 ] < [Mn(CO) 6 ] < [V(CO) 6 ]

y
Q.61 Which of the following complex shows ionization isomerism
(A) [Cr(NH3)6]Cl3 (B) [Cr(en)2 ]Cl2
(C) [Cr(en)3]Cl3 (D) [CoBr(NH3)5]SO4

B
Q.62 Which one of the following can show optical isomerism?
(A) CCl4 (B) K3[Cr(C2O4)3]
(C) K3[Fe(CN)6] (D) [Cr(NH3)6]Cl3

Q.63 The IUPAC name of Xe [Pt F6] is

(A) Hexafluoridoplatinate (VI) xenon (B) Xenon hexafluoridoplatinate (V)
(C) Xenon hexafluoridoplatinate (VI) (D) Xenonium hexafluoridoplatinum (V)

Q.64 The magnetic moment of [NiX4]2– ion is found to be zero. Then the metal of the complex ion is
(X = monodentate anionic ligand).
(A) sp3 hybridised (B) spd2 hybridised
(C) dsp2 hybridised (D) d2sp hybridised

Q.65 The number of ions formed, when bis (ethane-1,2-diamine) copper (II) sulphate is dissolved in water
will be
(A) 1 (B) 2 (C) 3 (D) 4

Q.66 A white precipitate of AgCl dissolves in NH4OH due to the formation of

(A) [Ag(NH3)2]Cl (B) [Ag(NH3)2]OH
(C) [Ag(NH4)2]2+ (D) [Ag(NH3)3]Br

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 Reconstruct Your Chemistry With Prince Sir

Q.67 In the complex FeK2[Fe(CN)6],

(A) Both Fe atoms are in the same oxidation state.
(B) Both Fe atoms are in different oxidation state.
(C) The coordination number of ion is 4.
(D) The complex is a high spin complex.

ri
Q.68 In the formula of brown ring complex [Fe (H2O)5 (NO)]SO4, the magnetic moment is 3.87 B.M. The
oxidation state of Fe and number of unpaired electrons present respectively are :
(A) 1+, 3 (B) 2+, 3 (C) 3+, 3 (D) 3+, 5

S
Q.69 The oxidation sate of iron in Na4[Fe (CN)5(NOS)] is

e
(A) 1+ (B) 2+ (C) 3+ (D) zero
Q.70 Which is true for [Ni(en)2]2+, Z(Ni) = 28? [3]

c
(A) paramagnetism, dsp2, square planar, C.N. of Ni = 2

in
(B) diamagnetism, dsp2, square planar, C.N. of Ni = 4
(C) diamagnetism, sp3, tetrahedral, C.N. of Ni = 4
(D) paramagnetism, sp3, square planar, C.N. of Ni = 4

Q.71

P r
Among Ni(CO)4, [Ni(CN)4]2– and NiCl 24 ,

(A) Ni(CO)4 and [Ni(CN)4]2– are diamagnetic and NiCl 24 is paramagnetic

(B) Ni(CO)4 and NiCl 24 are diamagnetic and [Ni(CN)4]2– is paramagnetic
[3]

y
(C) Ni(CO)4 is diamagnetic and [Ni(CN)4]2– and NiCl 24 are paramagnetic

B
(D) NiCl 24 and [Ni(CN)4]2– are diamagnetic and Ni(CO)4 is paramagnetic.

Q.72 Geometrical isomerism in coordination compunds is exhibited by [3]

(A) Square planar and tetrahedral complexes (B) Square planar and octahedral complexes
(C) Tetrahedral and octahedral complexes (D) Squre planar, tetrahedral and octahedral complexes

Q.73 Which of the following is not optically active? [3]

(A) [Co(en)3]3+ (B) [Cr(ox)3]3– (C) cis-[CoCl2(en)2]+ (D) trans-[CoCl2(en)2]+

Q.74 Arrange the following in order of decreasing number of unpaired electrons: [3]
(I) [Fe(H2O)6]2+ (II) [Fe(CN)6]3– (III) [Fe(CN)6]4– (IV) [Fe(H2O)6]3+
(A) IV, I, II, III (B) I, II, III, IV (C) III, II, I, IV (D) II, III, I, IV

Q.75 For which of the following dn configuration of octahedral complex (es), can not exist in both high spin
and low spin forms. [3]
(I) d3 (II) d5 (III) d6 (IV) d 8

(A) II & III (B) I & III (C) I & IV (D) III & IV

35
 Reconstruct Your Chemistry With Prince Sir
Q.1 A Q.2 A Q.3 A Q.4 B
Q.5 A Q.6 B Q.7 D Q.8 A
Q.9 D Q.10 A Q.11 A Q.12 A Q.13 C Q.14 B
Q.15 B Q.16 D Q.17 C Q.18 C Q.19 C Q.20 D
Q.21 C Q.22 B Q.23 B Q.24 C Q.25 D Q.26 D
Q.27 B Q.28 C Q.29 C Q.30 D Q.31 B Q.32 B

ri
Q.33 D Q.34 B Q.35 B Q.36 C Q.37 C Q.38 D
Q.39 A Q.40 A Q.41 B Q.42 D Q.43 B Q.44 A
Q.45 A Q.46 A Q.47 C Q.48 C Q.49 B Q.50 B
Q.51 C Q.52 C Q.53 C Q.54 C Q.55 B Q.56 C

S
Q.57 C Q.58 B Q.59 C Q.60 B Q.61 D Q.62 B
Q.63 B Q.64 C Q.65 B Q.66 A Q.67 A Q.68 A

e
Q.69 B Q.70 B Q.71 A Q.72 B Q.73 D Q.74 A
Q.75 C

in c
P r
B y

36