COMPLEX COMPOUNDS

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COMPLEX COMPOUNDS
 Secondary valency (Non-Ionisable valency)
SYNOPSIS
i) It is satisfied by anions or neutral molecules
Co-ordination Compounds or rarely with cations. The groups satisfying
 Double Salt : secondary valencies are called ligands.
1) Double salts exist only in solid state and ii) The number of secondary valencies is equal
dissociate into ions in water to coordination number.
2) They lose their identity in solution. iii) It is represented by thick lines while writing
3) The properties of double salt are essentially the structure of the complex.
the same as those of the constituent compounds  In some complexes the same groups satisfies
4) In double salts, metal ion exhibit their normal both primary and secondary valencies.
valency.  The ligands are directed in space around the
5) Double salts contain ionic bonds central metal atom in different ways. This leads
to a definite geometry to the molecule.
Ex: i) KCl . MgCl2 .6 H 2O (Carnallite)
ii) K 2 SO4 . Al2 ( SO4 )3 .24 H 2O (Potash alum) Colour Formula
No. of ions
in solution
iii)FeSO4 . (NH4)2 SO4 . 6H2O (Mohr’s salt)
 Coordination compound : Yellow CO NH 3 6  3Cl 
3
4 ions
1) They exist in the solid state as well as in
solution. Purple COCl NH 3 5  2Cl 
2
3 ions
2) They donot completely lose their identity in
solution. COCl2 NH 3 4  Cl 

Green 2 ions
3) The properties of coordinate compounds are
different from the constituent compounds. 
Violet COCl2 NH 3 4  Cl  2 ions
4) In coordination compound, metal ion is
surrounded by a number of anions or neutral
molecules. The metal ion exhibits more than Complex
No. of
6 Werner structure
ligands
its normal valency. Octahedral
5) Coordinate comounds may have ionic as well –
1. Three Cl ions satisfy primary valency NH3 NH3 NH3
2. Six NH3 species satisfy secondary valency
as coordinate bonds. COCl36NH3 6
3. Ions in solution = 4 Cl– CO
+3
Cl–

Ex: K4[Fe(CN)6], K3[Fe(CN)6], Na3  Ag  S 2O3 2  4. AgCl molecules precipitated on adding

AgNO3 = 3 AgCl = 3
NH3 NH
3
NH3
–
Cl
 The transition metal ions form co-ordinate –
5. Ionisable Cl = 3

compounds because Octahedral

–
1. Two Cl satisfy primary valency
i) They have small size. COCl35NH3 6
–
2. One Cl satisfy both primary and NH3 NH3 NH3
ii) They have high nuclear charge secondary valency
– +3 –
3. 5NH3 satisfy secondary valency Cl CO Cl
iii) They have vacant d-orbitals 4. No of ions in solution = 3
iv) They can accept lone pairs of electrons. 5. AgCl molecules precipitated on adding
Cl–
NH3 NH3

 Werner’s Theory: According to Werner AgNO3 = 2

6. Ionisable Cl– = 2
(father of Co-ordination chemistry) transition 1. Octahedral NH3 NH3
metals possess two types of valencies. –
2. 2Cl & 4NH3
3. One Cl satisfies
a) Primary valency (Ionisable valency) COCl34NH3 6
4. No of species in
Cl– CO+3 Cl–

b) Secondary valency (non ionisable valency) 5. AgCl molecules

– NH3 NH3
Cl

–
6. Ionisable Cl = 1
Primary Valency (Ionisable Valency)
1. Octahedral NH3 NH3
i) It is referred to as oxidation state. –
2. The three Cl ions and 3NH3 satisfy secondary
ii) It is satisfied by only anions. COCl33NH3 6 valency Cl
–
CO
+3
Cl
–

3. No. of species in solution = 1

iii) It is represented by dotted lines while writing 4. AgCl molecules precipitated = nil
– NH3
the structure of complex. 5. Ionisable Cl– = 0 Cl
 COMPLEX COMPOUNDS
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Defects in Werner’s Theory Definitions of Some Important Terms
 This theory does not relate the electronic in co-ordination Compounds
configuration of metal with the formation of the Oxidation number of central atom: The
complex. oxidation number of the central atom in a
 It is known now that the metal tries to acquire complex is defined as the charge it would carry
the nearest inert gas configuration during the if all the ligands are removed along with the
formation of complex electron pairs that are shared with the central
 This theory does not explain the reason for the atom. It is also called primary valency.
colour of the complex  The oxidation number is represented by a
 This theory does not explain the magnetic Roman numerical in parenthesis after the name
behaviour of complexes. of the metal.

W.E-1:When excess of silver nitrate solution is Coordination number: The coordination

added to aqueous solution containing 0.1 number (CN) of a metal ion in a complex can
be defined as the number of ligand directly
molar CoCl3 .xNH 3 . If 43.05 g of silver bonded to metal ion through coordinate bonds
chloride precipitated, then x value is (or)  bonds.
43.05  The co-ordination number is generally 2, 4 (or)
Sol. nAgCl   0.3 6, ocassionally 8 (in Osmium complexes).
143.5
 It is equal to the number of monodentate ligands
0.1 mole of CoCl3 .xNH 3 gives 0.3 mole of which are bound to central metal atom or ion
AgCl . through a dative bond. It is also called secondary
valency.
1 mole of CoCl3 .xNH 3 gives 3 mole of AgCl  Shape of the complex species depends on its
IV is 3. SV of Co 3 is 6 and PV is 3. co-ordination number.
So, IV = PV, Hence x =6. Co-ordination Shape of the
IV=Ionisable valency, PV=primary valency Number Complexes
2 Linear
W.E-2: The secondary valence of Co  3 is 6. 3 Trigonal planar
Calculate the number of moles of AgCl Tetrahedral (or)
4 square planar
precipitated, when excess of AgNO3 solution
Square pyramidal (or)
is added to 1.5lit of 0.2M. CoCl3 .5 NH 3 5 trigonal bipyramidal
solution.
6 Octahedral
Sol. SV of Co  3 is 6 and it will be satisfied by five Pentagonal
7
NH 3 and one Cl  the remaining 2Cl  ions bi-pyramidal

satisfy IV so fomula is CoCl  NH 3 5  Cl2 .  Co-ordination Entity or Co-ordination

1 mole of this complex gives 2 mole of Cl  sphere: A coordination entity constitutes a
ions central metal atom or ion bonded to a fixed
number of ions or molecules. It is enclosed in
1.5 x 0.2 mole gives how many moles of Cl 
square bracket and is collectively termed as the
ions. coordination sphere. The ionisable groups are
1.5  0.2 written outside the bracket and are called
 2  0.6moles counter ions
1
 COMPLEX COMPOUNDS
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 A molecule or ion which donates only one pair
 In CoCl  NH 3 5  Cl2 complex,
of electrons is called monodentate ligand. The
CoCl  NH 3 5  is coordination sphere and monodentate ligand is said to have only one
co-ordinating center.
2Cl  ions are counter ions. Ex: CN  , HO  , NH 3 , H 2O
 Co-ordination entities are mainly two types.  A molecule or ion which donates two lone pairs
They are of electrons is called bidentate ligand. The
a) Mononuclear complexes bidentate ligand will have two co-ordinating
centers.
Ex: K 4  Fe  CN 6  , CrCl  H 2O 5  Cl2 Ex: 1) Oxalate ion 2) Glycinate ion
b) Polynuclear complexes 3) Ethylene diamine
 Bidentate ligand: contains two donor atoms
Ex:  Co 2  NH 3  6  OH  3  Cl3 Ex :- oxalate, ethylenediamine, DMG, carbonate,
 
glycinate
 Mono nuclear complexes are three types.  Tridentate ligand: contains three donor atoms
1) Neutral complexes : Diethylene triamine, iminodiacetate, 2,2’,2’’-
complex donot posses charge terpyride

Ex: Co  NH 3 3 Cl3  ;  Pt  NH 3 2 Cl4 
Tetradentate ligand: contains four donor
atoms. Triethylene tetramine
2) Cationic complexes :  Pentadentate ligand: contains five donor
Complex posses positive charge atoms. Ethylene diamine triacetate (EDTA)-3
Ex : Cu  NH 3 4  SO4 ; Co  NH 3 6  Cl3
3) Anionic complexes :
complex posses negative charge

Ex: K 4  Fe  CN 6  , K 3 CoCl6 
 Hexadentate ligand: contains six donor
Based on ligands types of complexes: atoms. (EDTA)-4 (ethylene diamine tetra acetate)
 Homoleptic complex: The complex in which
the central metal atom (or) ion bound with only
one kind of ligand.
4 3
Ex:  Fe  CN 6  ,  Co  H 2 O  6 
 Heteroleptic complex: The complex in which  Ambidentate Ligand: It contains two donor
the central metal atom (or) ion bound with more atoms but both atoms can’t form dative bond in
than one kind of ligand. single compound.
2
Ex: CO  NH 3 5 Cl  O
Ligand: An ion or a molecule which can donate M N M O N O
a pair of electrons to a metal atom or a metal O
ion and can form dative bond is called ligand. nitrito-N nitrito-C
They are Lewis acids.
M SCN
 Ligands are three types M NCS
Negative ligands Eg: Cl-, SO4-2, CN-, C2O4-2; etc., thiocyanato isothiocyanato
Neutral ligands Eg: H2O, NH3 etc., EDTA can acts a penta and hexa dentate ligand.
Positive ligands Eg : NO+, NO2+ So., it is called felxi dentate ligand.
COMPLEX COMPOUNDS
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 Chelating ligands: A multi dentate ligand  No characteristics suffix for neutral
simultaneously coordinate to metal ion through ligands.
more than one sigma bond, a ring like structure Ex: NH CH CH NH - Ethylene diammine
2 2 2 2
obtained. which is called Chelate and ligand is
called Chelating ligand. C6 H 5 N - Pyridine
 Chelating effect: Due to this stability of PH 3 - Phosphine
 C6 H 5 3 P
complex increases.
- Triphenylphosphine
2
Ex : Cu  en 2  is less stable because it forms H 2O - aqua (or) aquo
1
only two rings.  Fe  EDTA   is more stable
NO - Nitrosyl
NH 3 - ammine
because it forms five rings.
CS - Thiocarbonyl
Chelate contains 6 donor atoms are less stable
due to steric hinderance. CO - Carbonyl
NS - Thionitrosyl
 Importance of Chelates: Chelates used in  Suffix for negative ligand is ‘o’.
(i) softening of hard water
Ex: Cl  - Chloro, OH  - hydroxo
(ii) separation of lanthanides and actinides.
(iii) estimation of Ni +2 , Mg +2 , Cu +2 ions NO2 - Nitrito, CO32 - Carbonato
qualitatively.
C2O42 - Oxalato, C6 H 5COO  - Benzoato
 Central atom/ion: In a coordination entity, the
Br  - Bromo, I  - Iodo, F  - Flouro
atom/ion to which a fixed number of ions/groups
are bound in a definite geometrical arrangement SO42 - Sulphato, O22 - Peroxo,
around it, is called the central atom or ion.
H  - Hydrido, NH 2 - amido,
 For example, the central atom/ion in the
coordination entities: [NiCl 2(H 2 O) 4 ], NH 2 - Imido C2O42 - Oxalato etc..
[CoCl(NH 3 ) 5 ] 2+ and [Fe(CN)6 ] 3– are Ni2+ ,  Suffix for positive ligand is ‘ium’.
Co3+ and Fe3+, respectively. These central atoms/
ions are Lewis acids. Ex: NO2 - Nitronium, Cl  - Chloronium

IUPAC nomenclature NO  - Nitrosonium, N 2 H 5 - Hydrazinium
 Order of Naming of Ions: The positive ion  Order of Naming Ligands:If more than one
is named first followed by the negative ion. different kinds of ligands are present in a
compound, their names should be written in
4
Ex: K 4  Fe  CN 6   4 K    Fe  CN 6  alphabetical order.

Potassium hexacyano Ferrate (II) Ex :  Pt  Br  Cl  NO2  NH 3   is named
 Name of the non ionic (or) neutral complex must as ammine bromo chloro nitro platinate (II) ion.
be written in one word.  Numerical prefixes to indicate number of
Ex :  Ni  CO 4  - tetra carbonyl nickel (O). ligands: If more than one same kind of ligands
are present they are labled as di, tri, tetra, penta
 Naming the Co-ordination Entity: In
etc. Ex : Cr  NH 3 6  Cl3 -
naming the coordination entity, the ligands are
named first and then central metal ion. Hexaamminechromium(III) chloride.
 2
Naming of ligands : ligands are 3 types  Ni  CN 4  - Tetracyanonickelate(II)ion.
 COMPLEX COMPOUNDS
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 If the same ligand can donate lone pairs from  Point of Attachment: When a ligand can
more than one centre, they are named as coordinate through more than one atom, then
bidentate, tridentate etc, depending on the the point of attachment of the ligand is indicated
number of lone pairs donated. by putting the symbol of the atom through which
Ex: NH 2CH 2CH 2 NH 2 . coordination occurs, after the name of the ligand.
 The number of bidentate, tridentate etc ligands Sometimes, different names are used for
is mentioned with bis, tris, tetrakis, etc. If they alternative modes of attachment.
already contain di, tri, tetra etc. in their names. Ex: NO2 can co-ordinate through -N (or) -O.
Ex:  Pt Br2  NH 2 CH 2 CH 2 NH 2 2  Cl2 is If it co-ordinates through N, it is called nitrito
-N (or simply as nitro). On the other hand, if
named as dibromobis (1, 2-ethane diamine) it co-ordinates through -O, (-ONO-), it is called
Platinum(IV) chloride. nitrito-O.
 Ending Names: When the complex is anionic,
the name of the central metal atom ends with -  NO2 (through N) ONO  (through -O)
ate. For cationic and neutral complexes the Nitrito -N (or) Nitrito-O (or)
name of the metal is written without any Simply nitro Simply nitrito
characteristic ending.  SCN  (through -S)  NCS  - (through -N)
Ex: Cationic complex : thio cyanato (or) isothio cyanato (or)
Co  NH 3 6  Cl3 -Hexamminecobalt(III) thio cyanato-S thio cyanato-N
 
chloride Cationic Complexes
Ex :Neutral complex :  Co  NH 3 6  Cl3
 
 Ni  CO 4  - Tetracarbonylnickel(0) Hexamminecobalt (III) chloride
Ex :Anionic complex :
  Pt  Cl  NH   Cl
K  Pt Cl5  NH 3   -
 3 5
 3
Pentaamminechloroplatinum (IV) chloride
Potassium amminepentachloroplatinate(IV)
 If the complex is anion, the name of the metal  CrCl  NO2  NH 3 4  NO3
should be taken from latin language. Tetraamminechloronitrochromium(III) nitrate
Ex : Cu - Cuprum – Cuprate
  Pt  NH 3 6  Cl4
Sn - Stannum – Stannate  
Fe - Ferrum – Ferrate Hexammineplatinum(IV) chloride.
Pb - Plumbum – Plumbate
 Co  NH3   H 2O  Cl  Cl2
Ag - Argentum – Argentate  4 
Au - Aurum – Aurate Tetraammineaquachlorocobalt(III) chloride.

Cr - Chromium – Chromate
 Cr  H 2O 4 Cl2 
Ni - Nickel – Nickelate
Tetraaquodichlorochromium(III)ion.
Oxidation State of Central Metal ion:
The oxidation state of the central metal ion is   Ag  NH 3 2  Cl Diamminesilver(I) chloride.
designated by a Roman numerical (such as II,
III, IV) in the brackets at the end of the name of  Ti  H 2O 6  Cl3
 
the metal of the complex. Hexaaquotitanium(III) chloride.
Ex : CoCl  NH 3 5  Cl2 -  Cr  NH 3 6  Cl3
 
Pentaamminechlorocobalt(III) chloride. Hexaamminechromium(III) chloride.
COMPLEX COMPOUNDS
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  Cu  en  2  SO4 Neutral Complex
 Co  NH 3 3 Cl3 
Bis(ethylenediamine)copper(II) sulphate.  
 Cu  NH 3 4  SO4 Triamminetrichlorocobalt(III)
  Pt  NH 3  Br2Cl2 
Tetraamminecopper(II) sulphate  2 
Diamminedibromodichloroplatinum(IV)
  Fe  H 2O 4  C2O4   SO4
2
 Cr  H 2O 3 Cl3  .3H 2O
Tetraaquaoxalatoiron(III) sulphate.  
Triaquotrichlorochromium(III)trihydrate.
  Fe  H 2O  NO   SO4
 5   Fe  CO 5 Pentacarbonyliron(O)
Pentaaquanitrasonium(I) sulphate
 Co  NH 3 3  NO2 3 
Anionic Complexes  
Triamminetrinitrocobalt (III)
 K 4  Fe  CN 6 
Isomerism in Complexes: Substances
Potassium hexacyanoferrate(II) having the same molecular formula but have
 Na2  Zn Cl4  Sodium tetrachlorozincate(II) different structures (or) properties are known as
isomers. The phenomenon of the existence of
 K 3  Fe  CN 5 NO  isomers is known as isomerism. It is two types
1) Structural isomerism 2) Stereo isomerism
Potassium pentacyanonitrosylferrate(II)
 Structural Isomerism: This isomerism arises
 K 3  Fe  CN 6  due to the difference in the structures of
complexes.
Potassium hexacyanoferrate(III)
 Ionisation Isomerism: Complexes which
 K 3 Cr  C2O4 3  have the same molecular formula but gives
different ions in solution are called Ionisation
Potassium trioxalatochromate(III)
isomers and the phenomenon is called ionisation
 K 3 CoCl2  C2O4 2  isomerism.
Potassium dichlorodioxalatocobaltate(III) Ex: Co  NH 3 5 SO4  Br and Co  NH 3 5 Br  SO4
 K2  HgI4  Potassium tetraIodomercurate(II).  Ionisation isomers are formed by the interchange
K 2  Pt Cl6 
of the position of ligands inside (or) out side
 the coordination sphere.
Potassium hexachloroplatinate(IV)  Ionisation isomerism arises, when the counter
 Na  Ag  CN 2  ions in a complex compound can also function
as ligands.
Sodium dicyanoargentate(I)  In the ionic complex compounds, the ion having
2 an opposite charge to that of the complex ion is
  Ni  CN 4  called counter ion.
Tetracyanonickelate(II) ion. i) K in K 4  Fe  CN 6 
 K 3 Cr  CN 6 
ii) Cl ions in Co  NH 3 6  Cl3
Potassium hexacyanochromate(III)
 The following pairs of compounds give different
 K 3 Co  CN 6  ions in solutions.
Potassium hexacyanocobaltate(III)  Co  NO3  NH 3 5  SO4 gives sulphate ions
 
 Na3  Ag  S 2O3 2  while Co  SO4  NH 3 5   NO3  gives nitrate
Sodium bis(thio sulphato)argentate(I) ions.
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 Linkage Isomerism: Complex with
 Co  NO3  NH 3 5  SO4 gives white
  ambidentate ligands shows this type of
precipitate with BaCl2 solution. isomerism. A mono dentate ligand with two (or)
more donar atoms is called ambidentate ligand.
Co  SO4  NH 3 5   NO3  cannot give white Ex: Co( NO )( NH ) 2 &
  
Co(ONO)( NH 3 )5 
2
2 3 5
precipitate with BaCl2 solution.
 Co-ordination Isomerism: It arises due to
  Pt Cl2  NH 3 4  Br2 gives Br ions. So it
 the mutual exchange of ligands between anionic
and cationic spheres.
can give light yellow precipitate with aqueous
AgNO3 solution. Ex: Co( NH 3 )6 Cr (CN )6  &

  PtBr2  NH 3  4  Cl2 gives Cl  ions. So it Co(CN )6 Cr ( NH 3 )6 

 Ligand Isomerism: This type of isomerism
can give white precipitate with aqueous AgNO3
arises due to the presence of isomers of the
solution.
ligands in different isomers of the complex
 Co  SO4  NH 3 5  Br is red coloured and it compound.
 
3
gives Br  ions, where as Co Br  NH 3 5  SO4 Ex :  Co  H 2 NCH 2 CH 2 CH 2 NH 2  3 
is violet coloured and it gives sulphate ions.
3
 Hydrate Isomerism: Hydrate isomerism is a  Co  CH 3CH - CH 2  
&   | |  
special type of ionization isomerism. This type
  NH 2 NH 2  3 
of isomerism arises due to the presence of water
molecules in and outside the coordination  Stereo Isomerism: Isomers which have the
sphere. same position of atoms (or) groups but differ in
 This type of isomers differ in number of water the spatial arrangements around the central atom
molecules as ligands and as hydrated molecules. are called stereo isomers and the phenomenon
Ex : CrCl3 .6 H 2O molecular formula has four is called stereo isomerism. It is classified into
possible isomers. They are two types.
(a) Geometrical isomerism
Cr  H 2O 6  Cl3 - violet coloured;
  (b) optical isomerism.
Cr  H 2O 5 Cl  Cl2 .H 2O - light green Geometrical Isomerism: Geometrical
 
isomerism is due to ligands occupying different
coloured
positions around the central metal atom (or) ion.
CrCl2  H 2O 4  Cl.2 H 2O - dark green  When two identical ligands occupy adjacent
coloured positions, the isomer is called cis-isomer.
 When two identical ligands occupy opposite
CrCl3  H 2O 3  .3H 2O - brown coloured
  positions, the isomer is called trans-isomer.

In the same manner CoCl3  H 2O 6 complex
Geometrical isomerism is very much common

in coordination number 4 and 6 complexes.
has the isomers  Tetrahedral complexes cannot exhibit
CoCl  H 2O 5  Cl2 .H 2O ; geometrical isomerism.
 Square planar complexes of the type
CoCl2  H 2O 4  Cl.2 H 2O
Ma4 , Ma3b, Mab3 do not exhibit geometrical
and CoCl3  H 2O 3  .3H 2O . isomerism.
 COMPLEX COMPOUNDS
Jr Chemistry E/M
 Square planar complexes of the type
Ma2b2 , Ma2bc and Mabcd exhibit CH3 CH3
geometrical isomerism. C – NH2 NH2– C
H H and
Pt

Ex :  Pt  NH 3 2 Cl2 
CH3 CH3
C – NH2 NH2– C
H CH3

H CH3
Cl  Cl  C – NH2 NH2– C
CH3 H
Pt
H CH3
C – NH2 NH2– C
CH3 H

Cl  Cl
 Octahedral complexes
L1

L5 L2
L4 L1
M
M

L4 L3
L3 L2
L6
Cis Positions : 1,2; 2,3; 3,4; 1.4 Cis Positions : 1,2; 1,3; 1,4; 1,5; 2,3; 2,5;
Trans Positions : 1,3; 2,4 3,4; 4,5; 2,6; 3,6; 4,6; 5,6
Trans Positions: 1,6; 2,4; 3,5
 Mabcd type of complexes will have 3
geometrical isomers i.e. 2cis and 1 trans isomer  octahedral complexes of the type Ma6 , Ma5b ,
 Square planer complex having unsymmetrical Mab5 do not exhibit geometrical isomerism.
bidentate chelating ligands with general  Octahedral complexes of the type
n
formula  M  AB 2  exhibit geometrical Ma4b2 , Ma4bc and Ma3b3 complexes exhibit
isomerism geometrical isomerism.

Ex : CoCl2  NH 3 4 

NH3 Cl–

Ex: NH3 Cl– H3N NH3

CO3+ CO3+

 Square planer complex having symmetrical

bidentate ligands with general formula NH3 Cl– H3N NH3
n
 M  AA 2  can also exhibit cis-trans NH3 Cl–
isomerism Cis-isomer Trans-isomer

Ex:  Pt II  NH 2 CH  CH 3  CH  CH 3  NH 2 2 
2
 Ma3b3 type of complexes exhibits maridian and
facial type of isomers
 COMPLEX COMPOUNDS
Jr Chemistry E/M
b
NH3 NH3
a b
Pt Pt
M NO2
H2O NO2 H2O
a Cl Cl
b
d-form Mirror l-form
a  A pair of optical isomers which are non super
facial imposable mirror images are called enantiomers
or enantiomorphs.
b  An equimolar mixture of d-forms and l-forms
is called racemic mixture. Racemic mixtures
a a are optically inactive.
 Optical Isomers have almost identical physical
M and chemical properties.
 The optical isomers can be distinguished only
a b by their rotation of the plane polarised light.
 Optical isomers are also generally provided by
the octahedral coordination compounds having
b bidentate (or) polydentate ligands.
 Octahedral complexes with general formula  3
n n Ex: CoCl2  en  2  , Cr  C2O4 3  ,
 M  AA 2 a2  ,  M  AA 2 ab  ,
 2
n
 M  AA  a2b2  can exhibit geometrical Cr  NH 3  Cl2en  ;  Pt Cl2  en  
 2   2

isomerism. Here ' en ' represents H 2 NCH 2CH 2 NH 2

 Octahedralcomplexexcontaining unsymmetrical  Optical isomerism is shown by the complexes
bidentate chelating ligands with general formula having chiral structures. They rotate the plane
n
 M  AB 3  can exhibit geometrical of polarised light in opposite directions.
a) Complexes with C.N. = 4
isomerism.  Square planar complexes do not show optical
 Optical Isomerism: The compounds having isomerism.
Tetrahedral complexes with formula M  AB 2
same molecular formula but differ in the rotation

of plane polarised light are called optical isomers
and the phenomenon is called optical isomerism. can exhibit optical isomerism.
 The isomer which rotates the plane polarised  Octahedral complexes with general formula
 Ma2b2c2  ,  Ma2b2 cd  ,  Ma2bcde 
light to the right direction is called dextro (d)- n n n
and
form while the isomer which rotates the plane
 Mabcdef 
n
polarised light to left direction is called laevo can exhibit optical isomerism.
( l )-form.  Octahedral complexes containing symmetrical
 Co-ordination number four, tetrahedral bidentate ligands with general formula
complexes of the type ( M abcd ) exhibit optical n n
 M  AA 3  ,  M  AA 2  BB   can exhibit
isomerism.
optical isomerism.
Ex :  Pt  NH 3  H 2O  Cl  NO2  
 COMPLEX COMPOUNDS
Jr Chemistry E/M
Type of Geometry of Examples
Py 2+ Py 2+ hybridization complex

Cl Py Py Cl sp Linear or  Ag  NH 3 2  ,
Pt Pt
 4s 4 p 

Cl NH3 Cl diagonal  Ag  CN 2 
H3N
NH3 NH3 CN  2
Mirror
cis-l-isomer
 HgI 3 

cis-d-isomer
sp 2 Trigonal planar
 Octahedral complexes containing  4s 4 p  2

unsymmetrical bidentate ligands with formula

CN  3
n
 M  AB 3  ( both Cis & Trans ) can exhibit sp3 Tetrahedral  Ni  CO 4 
0

optical isomerism.
 4s 4 p  3
 Zn  NH 3 4 
2

 Octahedral complexes containing symmetrical

 ZnCl4 
2
bidentate and monodentate ligands with CN  4
CuX 4 
2
n
general formula Cis   M  AA 2 a2  ,
 MnX 4 
2
n
Cis   M  AA 2 ab  ,
 NiX 4 
2

n
Cis   M  AA  a2b2  , and X  Cl  , Br  , I 
2
Cis   M  AA  BB  a2 
n
are optically active. dsp 2 Square planar  Ni  CN 4 

 Octahedral complexes containing polydentate 3d x2  y 2

4 s 4 pz 4 p y   Ni  NH 3 4 
2

ligands are optically active. 2

CN  4 Cu  NH 3 4 

Ex: Co III  EDTA   .
CuCl5 
3
dsp 3 Trigonal

W.E-3: The number of stereo isomers of the given  3d z2

4s 4 p3  bipyramidal  Fe  CO 5 
0

compound is CN  5

Co  C2O4   NH 3 2  NO2 2  .


sp 3 d  SbF5  , IF5
2
Square

Sol. Four  4s, 4 p 4d  pyramidal

3
x2  y 2

CN  5
3
VBT of Co-ordination Compounds: d 2 sp 3 Inner orbital Cr  NH 3 6 
 The central metal atom or ion makes available
a number of empty s, p and d atomic orbitals 3d x2  y 2 
3d z 2 4s 4 p 3 octahedral  Mn  CN 6 
3

3
equal to its coordination number. These vacant CN  6  Fe  CN 6  etc
orbitals hybridise together to form hybrid
 FeF6 
3
orbitals. These hybrid orbitals are vacant, sp 3d 2 Outer orbital
equivalent in energy and have definite geometry.
The most common hybridizations in complex  4 s 4 p 4d 3
x2  y 2 
4d z 2 octahedral Co  H 2O 6 
2

are given. 2
CN  6  Ni  NH 3 6 
 COMPLEX COMPOUNDS
Jr Chemistry E/M
 Each ligands have atleast one sigma orbital Examples of Complexes
containing alone pair of electrons. 4
1.  Mn  CN 6 
 Vacant hybrid orbitals of the central metal atom
C o m p l e x / i o n :

or ion overlap with the filled (containing lone Electronic configuration and hybridisation of Mn 2 :
pair of electrons) sigma orbitals of the ligands
to form metal-ligand sigma bond. This bond is 3d5 4s 4p
coordinate bond. ×× ×× ×× ×× ×× ××
 If d orbitals are involved in the hybridisation
than that may be either inner (i.e., (n-1) d-orbital) d2sp3-hybridisation
or the outer (i.e., nd-orbital). Geometry : Octahedral
 If (n - 1)d orbitals are used for hybridization No.of unpaired electrons/paramagnetic
along with ns and np orbitals, such complex is character: 1-Paramagnetic.   1.76BM
called inner orbital complex. If nd orbitals are
3
used for hybridisation along with ns and np 2. Complex/ion :  Fe  CN   Fe3
 6
orbitals then it is called outer orbital complex.
Electronic configuration and hybridisation:
 Some times the unpaired (n-1) d-electrons
undergoes rearrangement and provides more 3d5
number empty orbitals, which is possible in ×× ×× ×× ×× ×× ××
presence of strong ligands such as
CO, CN  , NO2  , en, NH 3 , Py and EDTA. d2sp3-hybridisation
 The non-bonding electrons of central metal atom Geometry : Octahedral
or ion remain unaffected and do not take part in No. of unpaired electrons/paramagnetic
chemical bonding. character: 1-Paramagnetic.   1.76BM
 During complex formation, the Hund’s rule of 3

maximum multipliciy is strictly followed. 3. Complex/ion :  Fe  H 2O 6  Fe3

However, under the influence of strong ligands,
the electrons may be forced to pair up against Electronic configuration and hybridisation:
Hund’s rule (but only for (n-1)d orbits) 3d
5

 Complex containing unpaired electron (unpaired ×× ×× ×× ×× ×× ×× ××

electron of central metal atom or ion) is 3 2
sp d -hybridisation
paramagnetic in nature. If all the electrons of
metal atom or ion are paired, the complex is Geometry : Octahedral
diamagnetic in nature. No. of unpaired electrons/paramagnetic
Inner orbital complex, low spin complex, spin character: 5-Paramagnetic.   5.86BM
paired complex or covalent complex 4
4. Complex/ion :  Fe  CN 6  Fe 2
Hyperligated complex
Electronic configuration and hybridisation:
Outer orbital complex, high spin complex, spin
free complex, or ionic complex, Hypo ligated 3d6
complex ×× ×× ×× ×× ×× ××
 The spin only magnetic moment of the complex
can be calculated by the formula d2sp3-hybridisation
S  n  n  2  BM Geometry : Octahedral
No. of unpaired electrons/paramagnetic
( n = number of unpaired electrons ) character: 0-Diamagnetic
 COMPLEX COMPOUNDS
Jr Chemistry E/M
2
Complex/ion :  Zn  NH 3 4  Zn 2
2
5. Complex/ion :  Fe  H 2O 6  Fe2 9.
Electronic configuration and hybridisation: Electronic configuration and hybridisation:
6
3d
×× ×× ×× ×× ×× ××

3 2
sp d -hybridisation

Geometry : Octahedral Geometry : Tetrahedral

No. of unpaired electrons/paramagnetic No. of unpaired electrons/paramagnetic
character: 4-Paramagnetic.   4.85BM character: 0-Diamagnetic
2

Complex/ion : Co  NH 3 6 
3
3 10. Complex/ion :  Ni  CN 4  Ni 2
6. Co
Electronic configuration and hybridisation:
Electronic configuration and hybridisation:

3d6 4s 4p
×× ×× ×× ×× ×× ××

d2sp3-hybridisation
Geometry : Square Planar
Geometry : Octahedral No. of unpaired electrons/paramagnetic
No. of unpaired electrons/paramagnetic character: 0-Diamagnetic
character: 0-Diamagnetic
11. Complex/ion :  NiCl4  Ni 2
2

7. Complex/ion: CoF6  Co3

3
Electronic configuration and hybridisation:
Electronic configuration and hybridisation:
6
3d
×× ×× ×× ×× ×× ××

3 2
sp d -hybridisation
Geometry : Tetrahedral
Geometry : Octahedral No.of unpaired electrons/paramagnetic
No. of unpaired electrons/paramagnetic character:
character: 4-Paramagnetic.   4.85BM 2-Paramagnetic
  2.8BM
8. Complex/ion: CuCl4  Cu 2
2

12. Complex/ion :  Ni  CO 4  Ni 0
Electronic configuration and hybridisation:
Electronic configuration and hybridisation:

Geometry : Tetrahedral
Geometry : Tetrahedral
No. of unpaired electrons/paramagnetic
No. of unpaired electrons/paramagnetic
character:1-Paramagnetic.   1.75BM character: 0-Diamagnetic
 COMPLEX COMPOUNDS
Jr Chemistry E/M
2
13. Complex/ion :  Pt  CN 4  Pt 2 Hence hybridisation is dsp 2 (square planar). But
Electronic configuration and hybridisation: Cl is weak field ligand. So, rearrangement of
d-electrons is not possible. Hence the

configuration of Ni 2 is
3d8
then hybridisation is sp3 (tetrahedral).
Geometry : Square Planar Effective atomic number (EAN)
No. of unpaired electrons/paramagnetic
 Effective atomic number (EAN) concept was
character: 0-Diamagnetic
introduced by Sidgwick to explain the stability
Limitations of VBT of complexes.
 It gives only the qualitative explanations for  The resultant number of electrons with the metal
complexes. atom or ion after gaining electrons from the
 It does not explain the detailed magnetic donar atoms of the ligands in a complex is called
properties of complexes. effective atomic number (OR)
 This thoery does not explain the spectral The total number of electrons present around
properties of coordination compounds. central metal ion in a complex is called effective
 It does not explain the thermodynamic and atomic number.
kinetic stabilities of different coordination  Sidgwick proposed that complex ion is stable.
compounds.
If EAN is equal to the atomic number of the
 It does not distinguish between weak and strong
nearest noble gas element.
ligands.
 EAN of a central metal can be calculated by the
 It does not make exact predictions regarding
terahedral or square planar coordinations entities following formula.
with co-ordination number is 4.  EAN  Z  x  n  y
x = charge of metal ions
W.E-3: The spin only magnetic moment of n = co-ordination number ; y =2
 FeBr4 

is 5.92 BM. Predict the geometry of Ex. (1)In K  Fe  CN   complex
4 6
complex ion.
EAN of Fe  26  2  6  2  36 .
Sol. Secondary valence of Fe 3 ion is 4. So,
3
complex is square planer  dsp  or tetrahedral
2 2)In Co  NH 3 6  complex ion

 sp  .
3
Br is weak field ligand so,
EAN of Co  27  3  2  6  36
rearrangement of d-electrons is not possible. 3)In  Ni  CO 4  complex
Hence complex is tetrahedral ( sp -3
EAN of Ni  28  0  2  4  36
hybridization). 2
4)In  Ni  CN  4  complex ion
2
W.E-4:  Ni  CN 4  is inner complex but
EAN of Ni  28  2  2  4  34
 NiCl4 
2
is outer complex. Give the reason. 3
5)In  Fe  CN 6  complex ion
2
Sol. CN  is strong field ligand. So. in  Ni  CN 4  EAN of Fe  26  3  2  6  35
6)In K 2  Pt Cl6  complex
ion Ni 2 configuration is
EAN of Pt  78  4  2  6  86  Rn 
8
3d
 COMPLEX COMPOUNDS
Jr Chemistry E/M
 In some complexes, the EAN is not equal to the  In a free metal atom, all five orbitals of d-sub
atomic number of the nearest inert gas. Yet they shell have same energy. They are called
are stable. degenerated orbitals.
2 When ligands approach the central metal atoms,
Ex: K 3  Fe  CN 6  ,  Ni  CN 4  . the electrons of d-orbitals of metal suffer
repulsions by lp of ligands as a result digeneracy
W.E-5: If  AuCl6 
y
follows EAN rule, then the
is broken and d-orbitals are split into two sets
oxidation state of Au is (At. no. of Au =79 of orbitals.
and At. no. of Rn =86).  a) Three of d-orbitals i.e., d xy , d yz and d zx which
Sol. EAN = Z - x + n x y are oriented in between the co-ordinate axes are
86 = 79 - x + 6 x 2 ; x = +5
called t2 g -orbitals.
W.E-6: If Ni  CO  x follows EAN rule, then x -  b) The other two d-orbitals i.e., d x2  y 2 and d z 2
value is which are oriented along the axes are called
Sol. EAN = Z - x + n x y
eg -orbitals.
36 = 28 - 0 + n x 2 ; n = 4.
 This spliting of d-orbitals of metal ion under
Formula of compound is  Ni  CO  4  . the influence of approaching ligands is called
crystal field spliting. It is designated by  and
Crystal Field Theory (CFT) is called crystal field splitting energy.
 This theory is based on theoretical work of Bethe  The decreasing order of field strength among
& Van Vleck on interaction of ionic crystals. some of the ligands are
 Ligands are either anion or neutral molecule Weak field ligand
containing atleast one lone pair of electron. The
anions are regarded as negative point charges. I   Br   SCN   Cl   S 2  NO3
The neutral ligands are regarded as point dipoles.  F   OH   ox 2  O 2  H 2O
 The neutral ligands are polarised by positive
charges of metal ion. Strong Field ligands
NCS   Edta 4  py  NH 3  en
 dipy  o  phen  NO2   CN   CO
 Central metal ion is surrounded by anions or
neutral ligands. For d 4 ions, two possible patterns of electron
distribution.
+
+ 1) If  0  p, the fourth electron enters one of
– – –
–
the eg orbital giving the configuration t2g
3 1
eg .
– M
+
– M
+

–
– Ligands for which  0  p are known as weak
– – + field ligands and form high spin complexes.
+ –
2) If  0  p , it becomes more energetically
+
favourable for fourth electron to occupy a t2 g
 The electrostatic attraction between nucleus of
orbital with configuration t2g
4 0
eg . Ligands which
cation and negative charge of ligands.
 Repulsive forces arise between lp of ligands, produce this effect are known as strong field
ligands and form low spin complex.
electrons of d-orbitals of central metal atom.
 COMPLEX COMPOUNDS
Jr Chemistry E/M
Crystal Field Splitting in octahedral In this situation, the t2 g set of orbital lie
and tetrahedral complexes relatively nearer to the approaching ligands and
 In octahedral complexes, the six ligands therefore t2 g set of d-orbitals have higher energy
approach the central metal ion along the co-
than eg set of orbitals.
ordinate axes i.e., the axes of d x2  y 2 and d z 2
 Relationship between  t and  0 is given as ;
orbitals. Consequently, the eg set of orbitals has
higher energy than t2 g orbitals. t 
4
o
9
 In tetrahedral complex, four ligands may be
imagined to occupy the alternate corners of the  While entering electrons into d-orbitals after
cube and the metal ion at the centre of the cube. splitting in ligand field, Hunds and pauli’s
principle to be followed.

weak

W.E-7:Arrange the following in the increasing d 10  6  0.4  4  0.6  0 0

order of stabilization energy of following in d 10  d 9  d 2  d 4  d 5
presence of strong field ligands.
Sol. d 2  2  0.4  0  0.6  0.8 0 W.E-8: Give the stabilization energy of d 7
electrons in presence of strong and weak field
d  3  0.4  0  0.6  1.2 0
3
ligands.
Sol. Strong field ligands
d 4  4  0.4  0  0.6  1.6 0
SE  6  0.4  1  0.6  1.8 0
d  5  0.4  0  0.6  2 0
5
Weak field ligands
d 9  6  0.4  3  0.6  0.6 0 SE  5  0.4  2  0.6  0.8 0
COMPLEX COMPOUNDS
Jr Chemistry E/M
Factors Determining the Magnitude of Colouring Coordination Compounds
the Orbital Splitting Energy  : The  most of the transition metal complexes are
following factors influence the magnitude coloured in their solid or solution form. The
of  . transition metals have the property to absorb
Nature of ligand: certain radiations from the visible region of the
spectrum and as a result, the transmitted or
 The  value depends upon the nature of the
reflected light is coloured.
ligand.
 In the case of transition metal complexes,the
 The CFSE depends on the tendency of ligand to
energy difference between two sets of d-orbitals
interact with the central metal ion.
is very small. When visible light falls on them,
 The ligands which cause only small  value the electron gets raised from lower set of orbitals
are called weak field ligands while those which to higher set of orbitals.
cause a large  value are called strong field  In case of octahedral complexes the electron
ligands.
goes from set of d xy , d yz , d zx to set of d x2  y 2 and
 The ligands can be arranged in the increasing
field strength in spectrochemical series. d z 2 orbitals.As a result of absorption of some
Oxidation state of the metal ion: selected wavelength of visible light
 Higher the ionic charge on the central metal ion, corresponding to energy difference between
the greater the value of  . these sets of energy levels, the transmitted light
gives colour to complexes,
 The metal ion with higher oxidation state causes
larger  than is done by the ion with lower  3
For example, the complex Ti  H 2O 6  is
oxidation state.
purple.
  for the entity [Co(H2O)6] will be more than
3+

 In this complex, the metal ion has d 1

 for the entity [Co(H2O)6]
2+

because oxidation state of cobalt is +3 in the configuration. The electron in t2 g orbital is

first and +2 in the second. excited to one of the eg


Nature of the metal ion:
For the analogous entities within a group, 
d x2  y 2 
or d z 2 orbital by absorbing light equal

values differ. The  value for similar complexes to  0 .

in the same oxidation state increases by 30-50%
This may be expressed as
on going from 3d series (first transition series)
to 4d series (second transition series). This t2 g1eg 0  t2 g 0 eg1
increase is almost of the same amount (30-50%)
 The energy corresponding to this transition
on going from 4d-series (second transition
corresponds to green and yellow lights which
series) to 5d-series (third transition series). As
are absorbed from the white light, while the blue
a consequence of this, coordination entities of
and red portions are emitted. the solution of
second and third transition series have a greater
3
tendency to form low spin complexes as comlpex Ti  H 2O 6  , therefore, looks
compared to the first transition series.
purple.
Geometry of the coordination entity
 In octahedral complexes  vary from one metal
 The  value for tetrahedral coordination entities
ion to another and the nature of the ligands.
is about half the  value for octahedral entities
 Different complexes absorb different amounts
4
i.e.  t   0 of energies from visible region and exhibit
9 different colours.
 COMPLEX COMPOUNDS
Jr Chemistry E/M
 For example, three complexes of Co 3+ as 2 2
 Ni  H2O4 en aq  enaq  Ni  H2O2 en2  aq  2H2O
[Co(H2O)6]3+ ,[Co(NH3)6]3+ and [Co(CN)6]3-.
According to spectrochemical series, the crystal blue / purple
field splitting energies will be in the order of 2 2

Ni  H2O2 en2  aq  enaq  Ni en3  aq  2H2O
ligands as H 2O  NH 3  CN
Violet
[CO(H2O)6]3+ [CO(NH3)6]3+ [CO(CN)6]3+
These colour changes are observed due to the
0 value small Intermediate Large presence of different ligands in the complexes.
Excitation Rules for Writing the Formulae of
small Intermediate Large
energy(
Absorption Co-ordination Compounds
wavelength large Intermediate small  All mononuclear complex entities contain a
(
single central metal atom, which is symbolised
Colour Orange first.
Blue Violet
absorbed
 If more than one ligand of each type is present,
Colour Yellow
Blue Yellow they represented in the following order.
transmitted orange
negative, neutral, positive
Colour of Ex:-
Wave length Colour of
Coordination coordination
of light light
in correct formula :  Fe  NO    CO 3 Cl 
entity entity 2
absorbed(nm) absorbed (transmitted)
3–
[CO(CN)6] 310 Violet Pale yellow 2
Correct formula :  FeCl  CO 3 NO   .
3+
[CO(H2O)6] 475 Blue Yellow orange
 Complete co-ordination entity is enclosed in
[CO(H2O)
Blue green
square brackets. Different species present in the
3+ 500 Red
(NH3)5] formula are written continuously without
[Ti(H2O)6]
3+
510 Blue green Purple leaving space.
 Charge of anionic or cationic complex is
[COCl(NH3)5] Violet
4+
53.5 Yellow indicated outside the square brackets as a right
superscript.
[Cu(H2O)6]3+ 600 Red Blue
3
W.E-9:In Ti  H 2O 6  complex Ti 3 has only
 It may be noted that in the absence of ligands,
the crystal field splitting does not occur and one electron in 3d-orbital. Its spectrum shows
hence the substance is colourless. For example, a single absorption peak of 5000 A0 then
removal of water from [Ti(H2O)6]Cl3, on heating corresponding energy is
makes it colourless. Similarly, anhydrous CuSO4
N 0 .hc
is white but CuSO4.5H2O is blue in colour. Sol. E 
 The effect of the ligand on the colour of a 
complex may be illustrated by taking the
6.023 1023  6.63  1034  3  108
example of [Ni(H2O)6]2+. This is formed when =
nickel chloride dissolved in water. The aqueous 5 107
solution of the complex has green colour. If the = 239 kJ / mol
bidentate ligand, ethane-1,2-diamine (en) is
progressively added in the molar ratio of en : Ni Metal Carbonyls
as 1 : 1, 2 : 1 and 3 : 1, the following series of  Class of coordination compound known as metal
reactions occur resulting different colour carbonyls in which carbon monoxide (CO) acts
changes as : as ligand.
2 2  These are also called homoleptic carbonyls
 N i  H 2 O  6   a q   en  a q    N i  H 2 O  4 en   2 H 2 O
P a le b lu e
(compounds containing carbonyl ligands only).
COMPLEX COMPOUNDS
Jr Chemistry E/M
 These compounds contain both (ii) There is a  -overlap involving donation of
 and  character.. electrons from filled metal d-orbitals into vacant
Structure of metal carbonyls anti-bonding  * molecular orbitals of CO. This
 Tetracarbonyl nickel (0) is tetrahedral. results into the formation of M  C  bond.
 Pentacarbonyl iron (0) is trigonal bipyramidal. This is also called back donation or back
 Hexacarbonyl chromium (0) is octahedral. bonding.The metal to ligand bonding creates a
 Some carbonyls have metal-metal bonds. synergic effect which strengthens the bond
 Decacarbonyl dimanganese (0) is made up of between CO and the metal.
two square pyramidal Mn(CO)5 units joined
by Mn-Mn bond. Stability of Coordination
 Octacarbonyl dicobalt (0) has a Co-Co bond  Compounds in Solution: The stability of a
bridged by two CO-CO groups. complex in solution refers to the degree of
association between the two species involved
CO CO
OC in the state of equilibrium.
 The magnitude of the (stability or formation)
Ni Fe CO
equilibrium constant for the association,
OC CO OC quantitatively expresses the stability.
CO CO  we have a reaction of the type:
Ni(CO)4 Fe(CO)5
Tetrahedral Trigonal bipyramidal M  4 L  ML4 then the larger the stability
constant, the higher the proportion of ML4 that
exists in solution. Free metal ions rarely exist
CO in the solution so that M will usually be
CO CO CO CO
CO CO surrounded by solvent molecules which will
Cr compete with the ligand molecules, L, and be
OC Mn Mn CO successively replaced by them. we generally
OC CO
CO CO CO ignore these solvent molecules and write four
CO CO stability constants as follows:
Cr(CO)6
[Mn(CO)10]
Octahedral M + L  ML K1=[ML]/[M][L]

ML+L  ML2 K2=[ML2]/[ML][L]

ML2+L  ML3 K3=[ML3]/[ML2][L]

ML3+L  ML4 K4=[ML4]/[ML3][L]

where K1, K2, etc., are referred to as stepwise
stability constants.
Alternatively, we can write the overall stability
constant thus:
Bonding in Metal Carbonyls: The
bonding in metal carbonyls is described by the
M + 4L  ML4  4 = [ML4]/[M][L]4
following steps:  The stepwise and overall stability constant
(i) There is a donation of lone pair of electrons are therefore related as follows:
of carbon (of CO) into the suitable empty orbital  4 = K1 × K2 × K3 × K4 or more generally,,
of the metal atom. This is a dative overlap and
forms a sigma M  C bond.  n = K1 × K2 × K3 × K4 ....... Kn
 COMPLEX COMPOUNDS
Jr Chemistry E/M
2
W.E-10: Zn 2  2 NH 3   Zn  NH 3 2  ; K1  2 103 K 4  Fe  CN 6   4 K    Fe  CN 6 
4

2
 Zn  NH 3 2   2 NH 3  K 2  1.5  103 
Find out the instability constant ? Ex : Fe  6CN 
2

Sol. K C  K1.K 2  2  10 3  1.5  10 3  3  10 6  feebly dissociated 

Instability constant is inverse of stability
Imperfect or normal complexes: These are
constant
the compounds in which complex ion is less
1 1 stable and is reversibly dissociated to give
  3.3  105
K C 3  106 enough simple ions.
2
Application of Complexes: CuSO4 K 2 Cd  CN 4   2 K   Cd  CN 4 
solution, when mixed with aqueous ammonia, 
gives a deep blue complex soluble in water. This Ex : Cd 2  4CN 
is used in the identification of Cu 2 ion. It is  appreciably dissociated 
due to the formation of the complex
2
Based on reactivity complex are two types
Cu  NH 3 4   Labile complexes : Those complexes are
 Ammonium salts are identified by Nessler’s highly reactive, i.e., in which ligands can be
readily replaced by other ligands are called labile
reagent. It is a complex K 2  HgI 4  -a colourless complexes.
solution.  Inert complexes : Those complexes are less
 Fe(III) ion in group III is identified as reactive, i.e., in which the ligands cannot be
[Fe(NCS)6]3- ion which has blood red colour. readily replaced by other ligands are called inert
 In Photography the developing of negative is complexes.
based on complex formation.
C.U.Q
AgBr  2 Na2 S 2O3  Na3  Ag  S 2O3  2   NaBr
WERNER’S THEORY
 The extraction of silver, gold from their ores
1. The following does not give a precipitate
makes use of a complex compound formed by
either with AgNO3 or BaCl2
leaching their ores with NaCN solution.
1) [Co (NH3)5 Cl] SO4 2) [Co (NH3)3 Cl3]
 In the electroplating of Ag, large amounts of
silver are held as the complex, K[Ag(CN)2]. 3) [Co (NH3)4 Cl2]Cl 4) Co NH 3 2 Cl4 Cl
 Haemoglobin is a complex which contains Fe+2 2. Which of the following has highest molar
ions. conductivity?
 Chlorophyll is a complex which contains Mg+2 1) [Co (NH3)6] Cl3 2) [Co (NH3)5Cl] Cl2
ions. 3) [Co (NH3)4 Cl2] Cl 4) [Co (NH3)3 Cl3]
 Vitamin - B12 is a complex which contains Co3+ 3. Transition elements form complexes readily
ions. because
ADDITIONAL TOPICS i) Small size of cation ii) Large ionic Charge
iii) Vacant d orbitals
 Based on stability complexes are two types
The correct statements is / are:
Perfect or penetrating complexes These are
the compounds in which complex ion is fairly 1) i only 2) ii only 3) i & ii 4) i,ii,iii
stable and is either not dissociated or feebly 4. The ionizable valency of Ni in Ni(CO)4 is
dissociated in solution. e.g., 1) 2 2) 4 3) 0 4) 1
 COMPLEX COMPOUNDS
Jr Chemistry E/M
5. According to Werner’s theory transition 16. Which of the following is cationic complex
1) K 4  Fe  CN 6  2)  Ni  CO  4 
metals possesses
1) only one type of valency
2) two types of valencies 3)  Co  NH 3 3 Cl3  4)  Cu  NH 3 4  SO 4
3) three types of valencies 17. The no. of moles of AgCl obtained when
4) four types of valencies excess AgNO 3 is added to one mole of
6. The primary valency of the metal ion is [Cr(NH3)4Cl2]Cl
satisfied by 1) 1 2) 2 3) 3 4) 4
1) neutral molecules 2) positive ions 18. Ligand in a metal carbonyl complex is
3) negative ions 4) all the above 1) NH3 2) CO 3) CN- 4) SCN-
7. No of ionizable & non-ionizable Cl ions in 19. The no. of moles of AgCl precipitated when
excess of AgNO3 is mixed with one mole of
CoCl3 5 NH 3 representively aree [Cr(NH3)3 Cl3] is
1) 3, 0 2) 2, 1 3) 1, 2 4) 0, 3 1) 0 2) 1 3) 2 4) 3
8. Central metal ion in complex compound acts NOMENCLATURE
as
1) Lewis acid 2) Lewis base 20. IUPAC name of the complex CoCl3 5 NH 3 is
3) Arrhenius acid 4) Arrhenius base 1) Cobalt trichloride penta amonium
9. Which one of the following acts as a Lewis 2) Penta amine carbonyl chloride
base in complexes 3) Trichloro penta amino cobalt
1) CO2 2) BF3 3) NH3 4) BCl3 4) Pentaaminechlorocobalt  III  chloride

DEFINITION OF ISOMERISM IN COMPLEXES

CO-ORDINATION COMPOUNDS 21. The property of possessing atleast one atom
that is attached to four non-identical groups
10. Potassium ferrocyanide is an example for
is called
1) Complex salts 2) Normal salts 1. polarisation 2. chirality
3) Double salts 4) Basic salts 3. enantiomerism 4. meridionity
11. Example for a coordination compound is 22. A racemic mixture has a net rotation
1) KCl . Mg Cl2 . 6H2O 1. to right of original plane
2) K2 SO4.Al2(SO3).24 H2O 2. to left of original plane
3) CoCl3 . 6N H3 3. toright or left of original plane
4) Fe SO4 . (NH4)2 SO4 . 6 H2O 4. zero
12. In which of the following transition metal 23. Optical isomer have
complexes does the metal exhibit zero 1) property of chirality
oxidation state 2) almost identical chemical properties
1) [Co (NH3)6] Cl3 2) [Fe (H2O)6] SO4 3) almost identical physical properties
3) [Ni (CO)4] 4) [Fe (H2O)6] Cl3 4) all the above
13. The number of moles of ions produced when EFFECTIVE ATOMIC NUMBER
one mole of Potassium Ferricyanide is 24. The effective atomic number of iron in
dissolved in water is
3
1) 2 2) 4 3) 5 4) 6  Fe  CN 6  is
 
14. Metal-Isothiocyanato is indicated by
1. 34 2. 36 3. 37 4. 35
1) M-SCN 2)M-NCS 3)M-CNS 4)M-CSN
25. Which doesnot obey EAN rule
15. Number of chlorides satisifying secondary
valency in CoCl3 .4 NH 3 1) Fe  CO 5 2) K 4  Fe  CN 6 
1) 2 2) 3 3) 4 4) 1 3) Cu  NH 3  4  SO4 4) Co  NH 3 6  Cl3
 COMPLEX COMPOUNDS
Jr Chemistry E/M
26. The effective atomic number of central metal CFT
ion is wrongly calculated in the following 35. Which of the following system has maximum
complex? number of the unpaired electrons in an inner
1. In  Ni  CO 4  the EAN of Ni is 36
octahedral complex ?
1) d 4 2) d 9 3) d 7 4) d 5
2. In K 2  Ni  CN 4  the EAN of Ni is 36 36. In an octahedral crystal field, the correct set
of low energy orbitals are
3. In K 3  Fe  CN 6  the EAN of Fe 35 1) d xy , d xz , d x2  y 2 2) d x2  y 2 , d z 2

4. In Cr  NH 3 6  Cl3 the EAN of Cr is 33 3) d xy , d xz , d yz 4) d xy , d x2  y 2

27. According to Sidgwick’s effective atomic 37. For the same metal, stabilisation energies of
number rule the central metal acquires tetrahedral and octahedral complexes are
1. inert gas configuration related in presence of strong field ligands is
2. octet 3. duplet 4. quartet 1)  t   0 2)  t  4   0  6
VALENCE BOND THEORY AND SHAPES 3)  t  9   0  4 4)  t  6   0  4
OF CO-ORDINATION COMPOUNDS 38. The orbitals having lower energy in
28. The shape of the complex species will be tetrahedral complexes according to CFT are
square planar if its coordination number is
1) d xy , d yz , d z 2 2) d xy , d yz , d x2  y 2
1) 2 2) 6 3) 5 4) 4
29. Which of the following is outer orbital 3) d xy , d yz , d zx 4) d x2  y 2 , d z 2
complex
APPLICATION OF COMPLEXES IN
1) CoF6 
3
2) [Cu ( H 2O ) 6 ]2 QUALITATIVE ANALYSIS AND METAL
3) [Co( NH 3 ) 6 ]2 4) Both 1 and 2 CARBONYL COMPOUNDS AND STABILITY
OF CO-ORDINATION COMPOUNDS
30. sp 3d 2 hybridisation is present in 39. The metal which does not form poly nuclear
1)  CoF6  2) [ N i  C O  4 ]
3 carbonyl is
1) Mg 2) Fe 3) Cr 4) Co
2
3) [Co( NH 3 ) 6 ] 2
4)  Ni  CN 4  40. Nessler’s reagent is
31. The type of hybridisation present in 1) K 2 HgI 4 2) K 2 HgI 2 3) K 2 HgCl4 4) HgI 2
2
41. Among the following metal carbonyls, the
Cu  NH 3 4  ion is C-O bond order is lowest is
2)  Fe  CO 5 

1) sp3 2) dsp 2 3) sp 3 d 4) sp 3d 2 1) V  CO 6 
32. The shape of  CoF6 
3
3) Cr  CO 6 
is 
4)  Mn  CO 6 
1) Square Planar 2) Trigonal bipyramidal
3) Octahedral 4) Tetrahedral
33. The hybridisation of metal atom & geometry C.U.Q - KEY

of complex in  Ag  NH 3 2  aree 1) 2 2) 1 3)4 4) 3 5) 2 6) 3 7) 2
8) 1 9) 3 10) 1 11) 3 12) 3 13) 2 14) 2
1) sp, linear 2) sp2, linear
3) sp2, trigonal planar 4) sp, angular 15) 1 16) 4 17) 1 18) 2 19) 1 20) 4 21) 2
2 22) 4 23) 1 24) 4 25) 3 26) 2 27) 1 28) 4
34. The magnetic moment of  Ni  Cl 4  is
29) 4 30) 1 31) 2 32) 3 33) 1 34) 1 35) 1
1) 2.85 BM 2) 1.83 BM
36)3 37) 3 38) 4 39) 1 40) 1 41) 1
3) 4.86 BM 4) 5.95 BM
 COMPLEX COMPOUNDS
Jr Chemistry E/M
C.U.Q - HINTS 35. In an inner orbital complexes :

1. Co  NH 3 3 Cl3  cannot ionise. d 4  t24g eg0 , so two unapired electrons

2. Co  NH 3 6  Cl3 gives more number ions. d 9  t26g eg3 , so one unpaired electron
7. 2, 1 d 7  t26g e1g , so one unpaired electron
8. In any complex central metal ion acts as Lewis
acid {electron pair acceptor) and Ligands acts d 5  t25g eg0 , so one unpaired electron
as Lewis base {electron pair donar)
4
9. NH 3 acts as ligand. 37.  t  0
9
12. In metal carbonyl compounds the oxidation
number of metal is zero because CO is neutral. 40. Formula of Nessler’s reagent is K 2 HgI 4 .
3 41. As increase of electron density back bonding
13. K 3  Fe  CN 6   3K    Fe  CN 6  tendence of  bond increases, so C-O bond
= 4 moles order decreases.

17. Cr  NH 3 4 Cl2  Cl ionises gives one Cl  ion. LEVEL-I (C.W)

So it gives 1 mole AgCl ppt.
20. Pentaamminechlorocobalt(III) chloride. WERNERS THEORY
21. Chirality property 1. Which of the following is not a draw back of
22. Racemicmixture contains equimolar proportions Werner’s theory
of d and l forms. So net rotation is zero. 1) does not explain the valency of metal ions in
the complex
23. Optical isomers are differ towards rotation of
plane polarised light. 2) does not give any explanation for the colour
of complex compounds
24. EAN=[Z-oxidation number of central ion + 2 x
number of ligands] 3) does not explain the magnetic behaviour of
complex compounds
= 26 - 3 + 2 x 6 = 35
4) does not correlate electronic configuration of
25. EAN = 29 - 2 + 2 x 4 = 35
the metal with the formation of complex
So, it does not obeys EAN rule.
26. EAN = 28 - 2 + 2 x 4 = 34 DEFINITION OF
27. According to Sidgwick’s EAN rule. The central CO-ORDINATION COMPOUND
metal atom acquires inert gas configuration. 2. Which is a coordination compound ?
28. Shape of complex depends on coordination 1) Ferrous ammonium sulphate 2) Carnallite
number. If coordination number = 4, shape is
3) Potassium ferrocyanide 4) Gypsum
tetrahedral (or) square planar.
3. A q u e o u s

2
O)5 SO4]Cl gives
s o l u t i o n o f [ C o ( H

29. NH 3 strong field ligand,so it forms inner orbital precipitate with

complex. 1) BaCl2 (aq) 2) AgNO3 (aq)
30. F  is weak field ligand so it forms outer 3) both 1 and 2 4) neither 1 nor 2
complex. 4. Silver Chloride dissolves in excess ammonia
32. Coordination number 6. So shape is octahedral. due to the formation of a soluble complex
34. Cl  is weak field ligand so rearrangement of whose formula is
1) [Ag (NH3)] Cl 2) [Ag (NH3)2] Cl
electron is not possible. Hence Ni 2 ion
3) [Ag (NH3)3]Cl 4) [Ag (NH3)4] Cl
contains two unpaired electrons.
 COMPLEX COMPOUNDS
Jr Chemistry E/M
+2
5. Zn dissolves in excess of NaOH due to the VBT AND SHAPES OF
formation of COORDINATION COMPOUNDS
1) Soluble Zn (OH)2
2) Soluble Na2 [Zn (OH)4] 13. The hybrdisation of the complex [ NiCl4 ]2 is
3) Soluble Na [Zn (OH)3] 4) ZnO 1) sp3 2) dsp 2 3) sp 3 d 4) sp 3d 2
6. Example of neutral complex compound in the
2
following is 14. The complex Fe H 2O  5 NO   is formed
 
1) CoCl3 .6 NH 3 2) CoCl3 .5 NH 3
in the brown ring test for nitrates when
3) CoCl3 .4 NH 3 4) CoCl3 .3NH 3 freshly prepared FeSO 4 solution is added to
7. Which of the following releases metal slowly
aqueous solution of NO 3  followed by
which gives uniform coating in electroplating
is addition of con.H 2SO 4 . Select correct
1) metal salts 2) double salts statement about this complex.
3) complex salts 4) alums 1) Colour change is due to charge transfer
NOMENCLATURE 2) it has iron in +1 oxidation sate and
8. IUPAC name for the complex nitrosonium as NO 
 Cu  NH 3 4  SO 4 is 3) it has magnetic of 3.87 BM confirming three
unpaired electrons in Fe
1) cuprammonium sulphate 4) it has iron in +2 oxidation sate and
2) copper sulphate tetraammonia
nitrosonium as NO 
3) tetraamminecopper   sulphate
II 15. Which of the following is paramagnetic ?
4) copper ammonium  IV  sulphate 1) Ni  CO  4
2) Fe  CO  5

ISOMERISM 3) V  C O  6 4) Cr  CO 6
9. Which of the following does not exhibit 16. The number of ions formed when
optical isomer ? cupraammonium sulphate is dissolved in
1) Co  NH 3 3 Cl3  2) Co  en 3  Cl3
    water
1) 1 2) 2 3) 4 4) zero
3) Co  en 2 Cl2  Cl 4) Co  en  NH 3 2 Cl2  Cl
CFT
10. Co-ordination compounds  Pt  NH 3 3  NCS   17. Which of the following is correct
arrangement of ligands in terms of field
and  Pt  NH 3 3  SCN   are example of -- strength
isomerism
1) Cl   F   NCS   NH 3  CN 
1) Co-ordination 2) Ionization
3) Linkage 4) Optical 2) NH 3  F   Cl   NCS   CN 
11. Geometrical isomerism is observed in
1) Tetrahedral complex 3) Cl   F   NCS   CN   NH 3
2) Square planar complex 4) NH 3  CN   NCS   Cl   F 
3) Tined complexes 18. In which of the following octahedral
4) Planar triangle complexes complexes of cobalt (atomic number = 27) will
EFFECTIVE ATOMIC NUMBER the magnitude of  0 be the highest ?
12. Stable complex based on EAN rule
3 3
1) Co  C2O4 3  2) Co  H 2O 6 
1) K 4  Fe  CN 6  2) Co  NH 3 5 Cl  Cl2
3 3
3) Co  NH 3 6  4) Co  CN 6 
3)  Ni  CO 4  4) all the above
 COMPLEX COMPOUNDS
Jr Chemistry E/M
19. If 0  P , the correct electronic 8. IUPAC name of complex Cu  NH 3  4  SO4 is
configuration for d 4 system will be tetraamminecopper(II) sulphate.
( P =pairing energy)
12. EAN of  Ni  CO  4  = 28 - 0 + 2 x 4 = 36, So it
1) t24g eg0 2) t23g e1g 3) t20g eg4 4) t22g eg2
is stable
APPLICATION OF COMPLEXES IN 13. It is outer orbital complex. Coordination
QUALITATIVE ANALYSIS AND METAL number is 4. Shape is tetrahedral.
CARBONYL COMPOUNDS AND STABILITY 18. Strength of ligands
OF CO-ORDINATION COMPOUNDS C2O42  H 2O  NH 3  CN 
20. Ammonium ions are detected with
1) Nessler’s reagent 2) Borsch reagent 19. Weak field ligand
3) Tollen’s reagent 4) Fehling’s solution 23. K  K1.K 2 .
21.  Ph3 P 3 RhCl  is a familiar catalyst used in
1) hydrogenation of oils LEVEL-I (H.W)
2) hydrogenation of alkenes
3) dehydration of alcohols WERNERS THEORY
4) dehydration of aldehydes 1. The complex formed by the combination of
22. Metals those can be extracted with aqueous calcium ions and ethylene di amine tetra
solution of sodium cyanide as complexes are
acetate.  EDTA  Number of moles of
4
1) Au and Ag 2) Fe and Ag
3) Au and Hg 4) Hg and Fe calcium ions produced by disulving of one
23. Ag   NH 3  Ag  NH 3  ; K1  3.5  10 3
 mole of that complex in excess of water is

1) one 2) two 3) four 4) five
A g  N H 3   N H 3   A g  N H 3  2  ; K 2  1 .7  1 0  3


Then, the formation constant of DEFINITION OF

 CO-ORDINATION COMPOUND
 Ag  NH 3 2  from Ag  and NH 3 is
2. Which is a double salt?
1) 1.7  10 3 2) 5.92  10 6 1) Carnallite 2) Potassium ferrocyanide
3) 1.8  103 4) 1.7  107 3) Potasium ferricyanide 4) Nessler’s reagent
3. Bonds present in K4 [Fe (CN)6] are
LEVEL-I (C.W) - KEY 1) Only ionic 2) Only covalent
1) 1 2) 3 3) 2 4) 2 5) 2 6) 4 7) 3 3) Ionic and Covalent
8) 3 9) 1 10) 3 11) 2 12) 4 13) 1 14) 2 4) Ionic, covalent and coordinate covalent
15) 3 16) 2 17) 1 18) 4 19) 2 20) 1 21) 2 4. Copper sulphate solution forms blue
coloured complex with excess of ammonia.
22) 1 23) 2
Its formula is
LEVEL-I (C.W) - HINTS 1) [Cu (NH3)4]+3 2) [Cu (NH3)4]+2
3) [Cu (NH4)3]+2 4) [Cu (NH4)3]+3
3. Co  CN 4 SO4  Cl ionises and gives Cl  ion.
5. Which of the following cannot act as a ligand
Ag   Cl   AgCl  ppt  1) BF3 2) NH3 3) NO  4) CN 

4. AgCl  2 NH 3   Ag  NH 3  2  Cl 6. Alum in aqueous solution gives positive test

for
5. Zn 2  2 NaOH  Na2 ZnO2  H 2 A) K  B) Al 3 C) SO42 
Na2 ZnO2  2 H 2O  Na2  Zn  OH 4  1) A only 2) B only 3) A and B 4) A, B and C
 COMPLEX COMPOUNDS
Jr Chemistry E/M
7. Chelates are used in VBT AND SHAPES OF
1) Analytical chemistry 2) Water softning COORDINATION COMPOUNDS
3) Removal of Pb2 from the blood 14. The following solutions requires three moles
of AgNO3 for the complete precipitation of
4) All of these all the chloride ions present in it
NOMENCLATURE 1) One litre of 1M [Co (NH3)6] Cl3
2) Three litres of 1M [Co (NH3)4 Cl2] Cl
8. Hexaaquotitanium  III  Chloride is 3) One litre of 1.5M [Co (NH3)5 Cl] Cl2
represented as 4) All the above
15. AgCl dissolved in excess of NH 3 , KCN and
1)  Ti  H 2 O 6  Cl3 2)  Ti Cl 3  6H 2 O Na 2S 2O 3 solutions the complex produces
ions.
3)  Ti  H 2 O 5 Cl  Cl 2 4) Ti  H 2 O 3 Cl3 
  3
1.  Ag  NH3 2  ,  Ag  CN 2  &  Ag  S2O3 2 
9. IUPAC name of Li[AlH4] is
2 3 2
1) Lithium aluminium hydride 2.  Ag  NH 2  2  ,  Ag  CN  2  &  Ag 4  S 2 O3  5 
2) Lithium tetrahydrido aluminate [III] 2  2
3.  Ag  NH 3  2  ,  Ag  CN  2  &  Ag 2  S 2 O3  2 
3) Tetrahydride aluminium lithionate
 3 2
4) Aluminium lithium hydride 4.  Ag  N H 3  4  ,  Ag  C N  4  &  Ag 2  S 2 O 3  2 
16. The secondary valency of chromium in
ISOMERISM
10. Dipole moment will be zero in the complexes Cr  en 3  Cl3 is
2 1) 6 2) 3 3) 2 4) 4
1) Ni  CN  
 4
CFT
2) Cis  Pt NH 3  2 Cl 2  17. Stabilisation energy of octahedral complex
with d 7 configuration
3) Trans  Pt NH 3  2 Cl 2  4) Both 1 and 3 A) 1.8  0 with one unpaired electron
11. The number of geometrical isomers of B) 1.8  0 with three unpaired electrons
Co  NH 3 3  NO3 3  is
C) 0.8  0 with one unpaired electron
1) 0 2) 2 3) 3 4) 4 D) 0.8  0 with three unpaired electrons

12. For the given comlex CoCl2  en  NH 3 2  , 1) A and D 2) A and B 3) C and D 4) B and C
18. If  0  P , the correct electronic
the number of geometrical iosmers, the
number of optical isomers and total number confuguration for d 4 system will be ( p =
of isomers of all type possible respectively are pairining energy)
1) 2, 2 and 4 2) 2, 2 and 3 1) t24g eg0 2) t23g e1g 3) t20g eg4 4) t22g eg2
3) 2, 0 and 2 4) 0, 2 and 2
APPLICATION OF COMPLEXES IN
EFFECTIVE ATOMIC NUMBER QUALITATIVE ANALYSIS AND METAL
13. Which does not obey EAN rule? CARBONYL COMPOUNDS AND STABILITY
OF CO-ORDINATION COMPOUNDS
1) K 4  Fe  CN 6  2) K 3  Fe  CN 6  19. The ligand used in the identification of cupric
copper in the laboratory
3) Co  NH 3 6  Cl3 4)  Ni  CO 4  1) NH 3 2) I  3) CN  4) S 2O32
 COMPLEX COMPOUNDS
Jr Chemistry E/M
20. The cofiguration of an element ‘X’ is 4 s 3d .
1 10 ADDITIONAL QUESTIONS
The wrong statement regarding the element 1. Type of Pair of examples
‘X’ is isomerism
1) it forms complexes
A)Ionisation (a) Cr  H 2O 6  Cl3 and
2) it exhibits variable velency
3) it forms paramagnetic ions only
Cr  H 2O 5 Cl  Cl2 .H 2O
4) It can form coloured salts  
21. In the qualitative analysis of group 3 cations
Cr  NH 3 6  Co  CN 6 
blood red colouration is a test for B) Linkage (b)   
1) iron using cyanide as ligand & Co  NH 3 6  Cr  CN 6 
2) chromium using cyanide as ligand
3) iron using thiocyanide as ligand Co  NH 3 5  NO2   Cl2
 
C)Coordination (c)
4) chromium using thiocyanide as ligand & Co  NH 3 5  ONO   Cl2

LEVEL-I (H.W) - KEY Co  SO4  NH 3 5  Br

 
1) 2 2) 1 3) 4 4) 2 5) 1 6) 4 7) 4 D)Hydrate (d)
& Co  Br  NH 3 5  SO4
8) 1 9) 2 10) 4 11) 2 12) 2 13) 2 14) 4
15) 1 16) 1 17) 1 18) 1 19) 4 20) 3 21) 3 The correct match is
A B C D A B C D
LEVEL-I (H.W) - HINTS 1. a b c d 2. b a d c
formula of the compound is  Ca2  EDTA 
3. d c b a 4. d b c a
1.
2. COLUMN-I COLUMN-II
4. CuSO4  4 NH 3  Cu  NH 3 4  SO4 (Complex) (Geometry)
A)  Ni (CN )6 2  p) Tetrahedral
5. BF3 Lewis acid. It can’t donate the lone pair of
electrons. B)  ZnCl4 2  q) Trigonal
8. Hexaaquotitanium(III) chloride is given as
C) Co(en)3 3 r) Sqaure planar
Ti  H 2O 6  Cl3 .
D) Cu ( NO2 ) 4 4  s) square pyramid
13. EAN = Z  x  n  y ; Z=At number of metal ion,
t) Octahedral
x=charge of metal ion, n= secondary valency
A B C D A B C D
14. n = M x V
1) r p t p 2) r p t q,t
15. AgCl  2 NH 3   Ag  NH 3  2  Cl 3) p q r s 4) p t q s
3. COLUMN-I COLUMN-II
AgCl  2 KCN  K  Ag  CN  2   KCl
(Equivalent (formula)
AgCl  2 Na2 S 2O3  Na3  Ag  S 2O3 2   KCl conductance)
17. For strong field ligands - A) 229 p)  Pt ( NH 3 )5 Cl  Cl3

CFSE   6  0.4  1 0.6   1.8 0 B) 97 q)  Pt ( NH 3 )3 Cl3  Cl

one unpaired electron C) 404 r)  Pt ( NH 3 )4 Cl2  Cl2
For weak field ligands D) 523 s)  Pt ( NH 3 )6  Cl4
CFSE   5  0.4  2  0.6   0.8 0 A B C D A B C D
three unpaired electrons 1) s p q r 2) r q s p
18. Strong field ligand. 3) r q p s 4) s p r q
 COMPLEX COMPOUNDS
Jr Chemistry E/M
4. COLUMN-I COLUMN-II 8. Match the lists I and II and pick the correct
(Complex) (  effective) matching from the codes given below
A) K3  MnF6  p) 1.70 List - I List - II
(complex) (Structure and magneticmoment)
B) K3 VF6  q) 2.8 
a)  Ag  CN 2  1) square planar and 1.73 BM
C) K2  Mn(CN )6  r) 3.8
3
D) K3 TiF6  s) 4.9 b) Cu  CN 4  2) Linear and zero
A B C D A B C D 4
c) Cu  CN 6  3) Octahedral and zero
1) s q r p 2) q s r p
2
d) Cu  NH 3 4  4) tetrahedral and zero
3) s q p r 4) p q r s
5. Match the following.
4
Set -I Set -II e)  Fe  CN 6  5) octrahedral and 1.73 BM
A) Co-ordination number 3 1) Pentagonal
bipyramidal 1) a-2,b-4,c-5,d-1,e-3 2) a-5,b-4,c-1,d-3,e-2
B) Co-ordination number 2 2) Trigonal 3) a-1,b-3,c-4,d-2,e-5 4) a-4,b-5,c-2,d-1,e-3
bipyramidal ASSERTION & REASON TYPE
C) Co-ordination number 5 3) Linear Two statements ‘A’ and ‘R’ are given below:
D) Co-ordination number 7 4) Trigonal planar Select your answers to these items using the
The correct matching is codes given below :
A B C D A B C D 1) Both A and R are correct and R is the correct
1) 4 3 2 1 2) 1 2 3 4 explanation of A
3) 4 3 1 2 4) 3 1 2 4 2) Both A and R are correct and R is not a correct
6. COLUMN-I COLUMN-II explanation of A
(Complex Ions) (No. of unpaired 3) A is true but R is false
electrons) 4) A is false but R is true
9. Assertion (A) : Among the cobalt (III)
A) CrF6 4  p)One 3
complexes Co  NH 3 6  is a diamagnetic but
B)  MnF6 4
q) Two
CoF6 
3
is paramagnetic.
C) Cr (CN )6  4
r) Three
3

D)  Mn(CN )6  4
s) Four Reason (R) : Hybridisation of Co  NH 3 6  is
t) Five sp 3d 2 where as hybridisation of Co in
A B C D A B C D
CoF6 
3
is d 2 sp 3 .
1) s t q p 2) q r s t
3) t q s p 4) p q r s 10. Assertion (|A) : The complex ion

7. COLUMN-I COLUMN-II cis  Co  en 2 Cl2  is optically active
(Complex) (O.N. of Co)
Reason (R) : It is an octahedral complex
A) Co( NCS )( NH 3 )5  (SO3 ) p) -1
11. Assertion (A) :  Ni  CO 4  is diamagnetic and
B) Na Co(CO)4  q) 0
tetrahedral in shape
C) Na4 Co( S2O3 )3  r) 1 Reason (R) : Hybridisation of the complex is
D) Co2 (CO)8 s) 2 dsp 2 .
t) 3
ADDITIONAL QUESTIONS - KEY
A B C D A B C D
1) 3 2) 1 3) 3 4) 1 5) 1 6) 1 7) 1
1) t p s q 2) q t s p
3) p t s q 4) q r s t 8) 1 9) 3 10) 2 11) 3
 9. COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
Jr Chemistry E/M
ISOMERISM
LEVEL-II (C.W)
7. The complexes Co ( NH 3 )6  Cr (C2O4 )3 
DEFINITION OF and Cr ( NH 3 )6  Co (C2O4 )3 
CO-ORDINATION COMPOUND 1) Geometrical isomerism
2) Ionization energy
1. Oxidation number of cobalt in K Co (CO )4  3) Co-ordination isomerism
is 4) Linkage isomerism
1) +1 2) +3 3) -1 4) -3 8. Which of the following complex or the
complex ion will show geometrical
[ EDTA]
4−
2. is a isomerism?
−
1) Monodentate ligand 2) Bidentate ligand 1)  Pt ( NH 3 )2 Cl2  2)  Pt ( NH 3 ) Cl5 
3) Quadridentate ligand 4) Hexadentate ligand
3+
3. ‘en’ is an example of a 3)  Pt ( NH 3 )5 Cl  4) Co ( NH 3 )6  Cl3
1) Monodentate ligand 2) Bidentate ligand 9. Which isomerism is exhibited by
3) Tridentate ligand 4) Hexadentate ligand Co ( NH 3 )3 ( H 2O )3  Cl3
NOMENCLATURE 1) Geometrical isomerism
2) Linkage isomerism
4. IUPAC name of K 2 [ PtCl6 ] is 3) Coordination isomerism
1) Potassiumhexachloroplatinum 4) Ionization isomerism
2) Potassiumhexachloroplatinum(IV) 10. Co ( NH 3 )4 ( NO2 )2  Cl exhibits
3) Potassium hexachloroplatinate(IV) 1) Linkage isomerism, ionization isomerism and
4) Dipotassium hexa chloro platinum geometrical isomerism
5. IUPAC name of 2) Ionisation isomerism, geometrical isomerism
and optical isomerism
 Pt ( NH 3 )3 Br ( NO2 ) Cl  Cl is 3) Linkage isomerism, geometrical isomerism
1) Triamminechlorobromonitroplatinum (IV) and optical isomerism
chloride 4) Linkage isomerism, ionization isomerism and
optical isomerism.
2) Triamminebromonitrochloroplatinum (IV)
11. Which one of the following is an example of
chloride
coordination isomerism?
3) Triamminebromochloronitroplatinum (IV)
chloride 1) Co ( NH 3 )5 Br  SO4 and
4) Triamminenitrochlorobromoplatinum (IV) Co ( NH 3 )5 SO4  Br
chloride
6. Tetrammine diaqua copper (II) hydrox 2) Co ( NH 3 )5 NO2  Cl2 and
ide is given by the formula
 Co ( NH 3 )5 ONO  Cl2
1) Cu ( NH 3 )4  (OH )2 .2 H 2O
3) Cr ( H 2O )6  Cl3 and
2)  Cu ( NH 3 )4 (OH )2  .2 H 2 O
Cr ( H 2O )5 Cl  Cl2 .H 2O
3)  Cu ( NH 3 )4 ( H 2O )2  (OH )2
4) Cr ( NH 3 )6  Co (CN )6  and
4)  Cu ( NH 3 )4 ( H 2O )(OH )2  Co ( NH 3 )6  Cr (CN )6 
JEE-MAIN-SR-CHEM-VOL-II COMPLEX COMPOUNDS
Jr Chemistry E/M
VBT CFT
20. For an octahedral complex, which of the
[ FeF6 ]
3+
12. has Fe atom .... hybridized with following d electron configuration will give
unpaired ........ electrons. maximum crystal - field stabilisation energy
1) d 2 sp 3 , 4 2) d 2 sp 3 ,5 1) High spin d 6 2) Low - spin d 4
3) sp 3 d 2 ,5 4) sp 3 d 2 ,3 3) Low spin d 5 4) High - spin d 7
13. How many EDTA molecules are required to APPLICATION OF COMPLEXES IN
make an octahedral complex with a Ca +2 QUALITATIVE ANALYSIS AND METAL
ion? CARBONYL COMPOUNDS AND STABILITY
1) two 2) six 3) three 4) one OF CO-ORDINATION COMPOUNDS
14. Which of the complexes will exhibit the 21. Chromium compound widely used in tanning
minimum paramagnetic behaviour of leather is
+2 +2 1) Cr2O3 2) Cr2O2Cl2 3) Cr2O3
1)  Fe ( H 2O )6  2)  Mn ( H 2O )6 
4) K2 SO4Cr2 ( SO4 )3 24H 2O
+2 +2
3) Cr ( H 2O )6  4)  Ni ( H 2O )6 
22. Wilkinsons catalyst,  Rh ( Ph3 P )3 Cl  is used
15. The expected spin only magnetic moments for for
4−
 Fe (CN )6  and [ FeF6 ] are
3− 1) Hydrogenation of oils
2) Hydrogenation of alkynes
1) 1.73and1.73 B.M 2) 1.73and 5.93 B.M 3) Hydrogenation of alkenes
3) 0.0 and1.73 B.M 4) 0.0 and 5.92 B.M 4) Polymerisation of alkenes
23. Coordination compounds have great
16. The volume (in mL) of 0.1M AgNO3 required importance in biological systems. In this
for complete precipitation of chloride ions context which of the following statements is
present in 30 mL of 0.01M solution of incorrect?
1) Chlorophylls are green pigments in plants and
Cr ( H 2O )5 Cl  Cl2 as silver chloride is close contain calcium.
to 2) Haemoglobin is the red pigment of blood and
1) 3 2) 4 3) 5 4) 6 contains iron.
17. Among the following ions which one has the 3) Cyanocobalamin is B12 and contains cobalt.
highest paramagnetism: 4) Carboxypeptidase-A is an enzyme and
3+ 2+
1) Cr ( H 2O )6  2)  Fe ( H 2O )6  contains zinc.

2+ 2+ LEVEL-II (C.W) - KEY

3) Cu ( H 2O )6  4)  Zn ( H 2O )2 
1) 3 2) 4 3) 2 4) 3 5) 3 6) 3 7) 3
18. Which of the following complexes is an outer 8) 1 9) 1 10) 1 11) 4 12) 3 13) 4 14) 4
orbital complex?
15) 4 16) 4 17) 2 18) 4 19) 2 20) 3 21) 4
4− 4−
1)  Fe (CN )6  2)  Mn (CN )6  22) 3 23) 1
3+ 2+
3) Co ( NH 3 )6  4)  Ni ( NH 3 )6  LEVEL-II (C.W) - KEY
EFFECTIVE ATOMIC NUMBER
2. (CH COO )
3
−
2
− N − CH 2 − CH 2 − N −
19. The EAN of cobalt in the complex ion (CH COO )
3
−
2
+
Co (en )2 Cl2  is 12. F − is weak field ligand so, its forms outer
1) 27 2) 36 3) 33 4) 35 complex.
 COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
Jr Chemistry E/M
14. H 2O is weak field ligand so, rearrangement 2. Which of the following is not chelating agent?
electron is possible 1) Thiosulphato 2) Oxalato
3) Glycinato 4) Ethylene diamine
1) n = 4 → µ = 4.85 BM
2) n = 5 → µ = 5.92 BM NOMENCLATURE
3) n = 4 → µ = 4.85 BM 3. IUPAC name of Na3 CoCl ( NO2 )5  is
4) n = 2 → µ = 2.8 BM 1) Sodium chloropentanitrocobaltate(III)
16. 1 - 2 2) Sodium cobaltnitrate
0.3 - ? 3) Trisodium chloropentanitro cobalt
0.3 4) Pentanitrocobalt (III) trisodium complex
× 2 = 0.6
1 4. The IUPAC name of the Wilkinsons catalyst
0.6  RhCl ( P Ph3 )3  is
0.6 = 0.1× X ; X = 0.1 = 6ml
1) Chlorotris (triphenylphopshine) rhodium (I)
17. 1) −n = 3 2) n = 4 3) n = 1 4) n = 0 2) Chlorotris (triphenylphosphine) rhodium (IV)
18. Ni +2 − 4 s 0 3d 8 rearrangement of electron is not 3) Chlorotris (triphenylphosphine) rhodium (0)
possible. So, hybridisation is sp 3 d 2 . 4) Chlotrotris (triphenylphosphine) rhodium (VI)
5. IUPAC name for the compound
20. High spin d 6 : t24g eg2
Co ( NH 3 )5 ( NO2 ) Cl2 is
CFSE = [0.4 × 4 − 0.6 × 2] ∆ 0
1)Nitrito-N-pentaammine cobalt (III)chloride
Low spin d 4 : t24g eg0 2)Nitrito-N-pentaammine cobalt (II) chloride
3) Pentaammine nitrito-N-cobalt (II) chloride
CFSE = [0.4 × 4] = 1.6∆ 0
4) Pentaammine nitrito-N-cobalt (III)chloride
Low spin d 5 : t25g eg0
ISOMERISM
CFSE = [0.4 × 5] ∆ 0 6. Both geometrical and optical isomerism are
shown by
High spin d 7 : t25g eg2 + 2+
1) Co (en )2 Cl2  2) Co ( NH 3 )5 Cl 
CFSE = [0.4 × 5 − 0.6 × 2] ∆ 0
+ 3−
22. Wilkinson’s catalyst is ( Ph3 P )3 RhCl 3) Co ( NH 3 )4 Cl2  4) Cr (ox )3 
(transform)
LEVEL-II (H.W) 7. Which of the following is not optically active?
3+ 3−
1) Co (en )3  2) Cr (ox )3 
DEFINITION OF
+
CO-ORDINATION COMPOUND 3) cis − CoCl2 (en )2 
1. An ambidentate ligand is one which
+
1) is linked to the metal atom at two points 4) trans − CoCl2 (en )2 
2) has two donor atoms but only one of them
has the capacity to form a coordinate bond. 8. Cis-trans isomerism is found in square planar
3) has two donor atoms but either of the two complexes of the molecular formula: (a and
can form a co-ordinate bond b are monodentate ligands)
4) forms chelate rings 1) Ma4 2) Ma3b 3) Ma2b2 4) Mab3
 JEE-MAIN-SR-CHEM-VOL-II COMPLEX COMPOUNDS
Jr Chemistry E/M
9. Which of the following isomeric pairs shows 14. A solution containing 2.675g of CoCl . 6NH
3 3
ionization isomerism?
−
(molar mass = 267.5 g mol ) is passed
1
1) Co ( NH 3 )6  Cr (CN )6  and
through a cation exchanger. the chloride ions
Cr ( NH 3 )  Co (CN ) 
 6  6 
obtained is solution were treated with excess
of AgNO3 to give 4.78 g of AgCl (molar mass
2) Cr ( H 2O )6  Cl3 and
= 143.5 g mol −1 ). The formula of the complex
Cr ( H 2O )5 Cl  Cl2 .H 2O is
(At. mass of Ag = 108 u)
3)  Pt ( NH 3 )2 Cl 2  and
1) CoCl3 ( NH 3 )3  2) CoCl ( NH 3 )5  Cl2
 Pt ( NH 3 )4  [ PtCl4 ]
3) Co ( NH 3 )6  Cl3 4) CoCl2 ( NH 3 )4  Cl
4) Co ( NH 3 )5 Br  SO4 and
2+
Co ( NH 3 )5 SO4  Br 15. The complex  Pt ( NH 3 )4  has... structure

VBT 1) square planar 2) tetrahedral

10. List - I List - II 3) pyramidal 4) pentagonal
A) Ti +3 1) Charge transfer phenomenon\ CFT
B) MnO4− 2) Impurities 16. Crystal field stabilization energy for high
spin d 4 octahedral complex is
C) F2 3) s-s transition
D) Gems 4) d-d transition 1) 0.6∆ 0 2) 1.8∆ 0 3) 1.6∆ 0 4) 1.2∆ 0
5) Excitation of electron \
APPLICATION OF COMPLEXES IN
The correct match which is responsible for
colour QUALITATIVE ANALYSIS AND METAL
1) A - 4, B - 1, C - 2, D - 5 CARBONYL COMPOUNDS AND STABILITY
2) A - 4, B - 1, C - 5, D - 2 OF CO-ORDINATION COMPOUNDS
3) A - 4, B - 5, C - 1, D - 2 17. Which of the following is antidote for lead
4) A - 5, B - 2, C - 3, D - 4 poisoning?
11. Co-ordination number of Cr is 6.A complex
1) CoCl3 2) Cis-platin 3) EDTA 4) DMG
entity with C2O4−2 en, superoxide as ligands
18. EDTA is used for the estimation of
is Cr (C2O4 )x (en ) y (O2 )z  . The ratio of x : y 1) Na + and K + ions 2) Cl − and Br − ions
: z is 3) Cu 2 + and Ag + ions 4) Ca 2 + and Mg 2+ ions
1) 1 : 1 : 2 2) 1 : 1 : 1 3) 1 : 2 : 2 4) 2 : 1 : 1 19. Wilkinson’s catalyst used as a homogeneous
12. The geometries of Ni (CO )4 and catalyst in the hydrogenation of alkenes
contains
Ni ( PPh3 )2 Cl2 are 1) iron 2) aluminium
1) both square planar 3) rhodium 4) cobalt
2) tetrahedral and square planar 20. Ziegler - Natta catalyst is
3) both tetrahedral
4) square planar and tetrahedral 1) Solution of SnCl4 + trialkylaluminium
13. What are the magnetic moment (in BM) for 2) Solution of TiCl4 + trialkylaluminium
Ni(II) ion in square planar and octahedral
geometry, respectively? 3) Solution of TiCl4 + trialkylchromium
1) 0 and 2.83 2) 2.83 and 2.83
4) Solution of SnCl4 + Tollen’s reagent
3) 0 and 1.73 4) 2.83 and 0
 COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
Jr Chemistry E/M
LEVEL-II (H.W) - KEY 3. A coordinate complex contains CO +3 , Cl −
1) 3 2) 1 3) 1 4) 1 5) 4 6) 1 7) 4 and NH 3 when dissolved in water, one mole
8) 3 9) 4 10) 2 11) 1 12) 2 13) 1 14) 3 of this complex gave a total of 3 moles of ions.
15) 1 16) 1 17) 3 18) 4 19) 3 20) 2 The complex is [EAM-2012]

LEVEL-II (H.W) - HINTS 1) Co ( NH 3 )6  Cl3 2) Co ( NH 3 )5 Cl  Cl2

11. C2O4−2 and en are bidentate ligands O2− is
3) Co ( NH 3 )4 Cl2  Cl 4) Co ( NH 3 )3 Cl3 
monotente ligand.
4. Identify the correct set [EAM-2013]
12. Hybridisations are sp3 and dsp 2
Molecule Hybridisation Shape
13. For square planar
1) PCl5 dsp 3 square pyramidal
→n=0 −2
2)  Ni (CN )4  sp3 tetrahedral
For octahedral
3) SF6 sp 3 d 2 octahedral
→n=2
4) IF3 dsp 3 pyramidal
2.675
14. Moles of the complex = = 0.01 5. Match the following [EAM-2014]
267.5
List-I List-II
4.78
moles of AgCl precipitated = = 0.033 3−
143.5 A) sp3 I) Co ( NH 3 )6 
Thus, 1 mole of the complex will precipitate
0.033 B) dsp 2 II)  Ni (CO )4 
AgCl = 3moles
0.01
C) sp 3 d 2 III)  Pt ( NH 3 )2 Cl2 
That means 1 molecule of the complex contains
3 ionizable Cl.
IV) (CoF6 )
−3
D) d 2 sp 3
Hence, the formula is Co ( NH 3 )6  Cl3
16. Weak field ligand V)  Fe (CO )5 

d 4 → t 23g , e1g 1) A-II, B-III, C-IV, D-I

2) A-II, B-III, C-I, D-V
CFSE = 3 × 0.4 − 1× 0.6 = 0.6∆ 0
3) A-III, B-II, C-IV, D-I
PREVIOUS EAMCET QUESTIONS 4) A-V, B-II, C-IV, D-III
1. CO ( NH 3 )5 SO4  Br and CO ( NH 3 )5 Br  SO4
6. Ti ( H 2O )6  Cl3 has Ti atom ___ hybridized
are a pair of ____ isomers [EAM-2008]
with unpaired ___ electrons. [EAM-2010]
1) Ionization 2) Ligand
3) Coordination 4) Hydrate 1) d 2 sp 3 ,1 2) d 2 sp 3 , 4
2. The solution of X having excess of caustic
potash is used to detect ammonia. Which of 3) sp 3 d 2 ,1 4) sp 3 d 2 ,3
the following is X [EAM-2011]
1) K 2 [ HgI 4 ] 2) CO ( NH 3 )6  Cl3 PREVIOUS EAMCET - KEY

3) K 3  Fe (CNS )6  4) CO ( NH 3 )5 SO4  Br 1) 1 2) 1 3) 2 4) 3 5) 1 6) 3

JEE-MAIN-SR-CHEM-VOL-II COMPLEX COMPOUNDS
Jr Chemistry E/M
6. Among the following which are ambidentate
LEVEL-III lignads ?
WERNER’S THEORY a) NO 2b) NO
−
c) EDTA
3
− 4-

1. One mole of the complex compound d) C O

2 e) SCN
4
2−
f) H NCH CH NH
−
2 2 2 2

Co ( NH 3 )5 Cl3 gives 3 moles of ions on 1) (a) and (b) 2) (c) and (d)
dissolution in water. One mole of the same 3) (a) and (f) 4) (a) and (e)
complex reacts with two moles of AgNO3 7. The number of donor sites in dimethyl
glyoxime, glycinato, diethylene triamine and
solution to yield two moles of AgCl ( s ) . The EDTA are respectively
structure of complex is 1)2,2,3 and 6 2) 2,2,3 and 4
1) Co ( NH 3 )4 Cl  Cl2 .NH 3 3) 2,2,2 and 6 4) 2,3,3 and 6

2) Co ( NH 3 )5 Cl  Cl2
NOMENCLATURE
8. The IUPAC name of the coordination
3) Co ( NH 3 )3 Cl3  2.NH 3
compound K 3  Fe (CN )6  is
4) Co ( NH 3 )4 Cl2  Cl.NH 3 1) potassium hexacyanoferrate (II)
2. The primary and secondary valencies of 2) potassium hexacyanoferrate (III)
chromium in the complex ion, 3) potassium hexacyanoiron (II)
dichlorodioxalatochromium (III), are 4) tripotassium hexacyanoiron(II)
respectively
1) 3,4 2) 4,3 3) 3,6 4) 6,3 ISOMERISM
3. In the complex with formula MCl3 .4 H 2O the 9. Which one of the following has largest
co-ordination number of the metal M is six number of isomers?
and there is no molecule of hydration in it. + 2+
1)  Ru ( NH 3 )4 Cl2  2) Co ( NH 3 )5 Cl 
The volume of 0.1M AgNO3 solution needed
2+ +
to precipitate the free chloride ions in 200ml 3)  Ir ( Ph3 )2 H (CO ) 4) Co (en )2 Cl2 
of 0.01M soltuion of the complex is
1) 40ml 2) 20 ml 3) 60 ml 4) 80 ml (R=alkyl group, en=ethylenediamine)
4. The molar ionic conductances of octahedral 10. Which of the following compounds shows
complexes. optical isomerism?
I) PtCl4 .5 NH 3 II) PtCl4 .4 NH 3 3− 3−
1) Cr (C2O4 )3  2) Co (CN )6 
III) PtCl4 .3 NH 3 IV) PtCl4 .2 NH 3
2+
3) Cu ( NH 3 )4  4) [ZnCl4 ]
2−
1) I<II<III<IV 2) IV<III<II<I
3) III<IV<II<I 4)IV<III<I<II
11. In which of the following pairs both the
DEFINITION OF complexes do not show optical isomerism?
CO-ORDINATION COMPOUND −3
5. The coordination number of a central metal 1) cis − Cr (C2O4 )2 Cl2  ,
atom in a complex is determined by
1) the number of ligands around a metal ion trans − Co ( NH 3 )4 Cl2 
bonded by sigma bonds
2) the number of ligands around a metal ion 2) Co (en )3  Cl3 , Cis − Co (en )2 Cl2  Cl
bonded by π -bonds
3)  PtCl2 ( en ) , [ NiCl2 Br2 ]
−2
3) the number of ligands around a metal ion
bounded by sigma and pi bonds both.
4) the number of only anionic ligands bonded 4) Co ( NO3 )3 ( NH 3 )3  , cis −  Pt (en )2 Cl2 
to the metal ion.
 COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
Jr Chemistry E/M
12. Of the following configurations, the optical 17. The correct order of magnetic moments (spin
isomers are only values in bohr magneton) among is
4−
1) [MnCl4 ] > [CoCl4 ] >  Fe (CN )6 
2− 2−

4−
2) [MnCl4 ] >  Fe (CN )6  > [CoCl4 ]
2− 2−

4−
3)  Fe (CN )6  > [MnCl4 ] > [CoCl4 ]
2− 2−

4−
4)  Fe (CN )6  > [CoCl4 ] > [MnCl4 ]
2− 2−

(Atomic numbers: Mn = 25, Fe = 26, Co = 27)

18. Which one of the following cyano complexes
would exhibit the lowest value of
paramagnetic behaviour?
3− 3−
1)  Fe (CN )6  2) Co (CN )6 
3− 3−
3) Cr (CN )6  4)  Mn (CN )6 

1) I and II 2) I and III 19. Which of the following statemants is not

3) II and IV 4) II and III correct ?
2−
13. The type of isomerism shown by 1) The complexes [ NiCl ] and  Ni (CN )  4
2−
4

Co ( NH3 )4 Br2  Cl is differ in their magnetic properties.

2− 2−
1) Optical and ionisaton 2) The complexes Ni (Cl )4  and  Ni (CN )  differ
4

2) Geometrical and optical in the state of hybridisation of nickel.

3) Geometrical and ionisation 2− 2−
4) Only geometrical 3) the complexes Ni(Cl)  and  Ni (CN )  differ
4 4

14. Which of the following doesn’t have optical in geometry.

isomer? 2− 2−
4) The complexes Ni (Cl )4  and  Ni (CN )  differ
1) Co (en )3  Cl3 2) Co ( NH 3 )3 Cl3 
4

in primary valancies of nickel.

3) Co (en )2 Cl2  Cl 4) Co (en )( NH 3 )2 Cl2  Cl 20. The species having tetrahedral shape is
2− 2−
1) [PdCl ]  Ni (CN 4 )  Pd (CN 4 ) 4) [ NiCl ]
2− 2−

VBT AND SHAPES OF 4

2) 3) 4

COORDINATION COMPOUNDS 21. 2−

 Ni (CN )4  , [MnBr4 ]
2−
and [FeF ] . Geometry, 6
3−

15. The complex K 3  Fe (CN )6  should have a hybridisation and magnetic moment of the
ions respectively are
spin only magnetic moment of
1) Tetrahedral ,square planar, octahedral :
1) 48BM 2) 2 5BM 3) 35BM 4) 6BM
sp3 , dsp 2 , sp3d 2 :5.9,0,4.9
16. Which one of the following complexes is an
outer orbital complex? 2) Tetrahedral ,square planar, octahedral :
4− 4− dsp 2 , sp3 , sp3d 2 :0,5.9,4.9
1)  Fe (CN )6  2)  Mn (CN )6 
3) Square planar, tetrahedral ,octahedral :
3+ 2+
3) Co ( NH 3 )6  4)  Ni ( NH 3 )6  dsp 2 , sp3 , d 2 sp 3 :5.9,4.9,0
4) Square planar, tetrahedral ,octahedral :
[Atomic numbers: Mn = 25, Fe = 26, Co = 27,
Ni = 28] dsp 2 , sp3 , sp3d 2 :0,5.9,4.9
JEE-MAIN-SR-CHEM-VOL-II COMPLEX COMPOUNDS
Jr Chemistry E/M
CFT 27. In Fe (CO )5 the Fe − C bond possess
22. Cr ( H 2O )6  Cl3 has a magnetic moment of 1) π − character only
3.83BM. The correct distribution of 3d 2) σ character only
electrons in chromium present in the complex 3) ionic character only
is 4) Both σ and π character
1
1
1) 3 d xy , 3 d 1yz , 3 d zx1 2) 3 d xy , 3 d 1yz , 3 d z12
LEVEL-III - KEY
1 1 1 1 1 1
3) 3d ( x2 − y 2 ) ,3d ,3d
4) 3d ,3d ( x2 − y 2 ) ,3d
z2 xz xy yz 1) 2 2) 3 3) 2 4) 2 5) 1 6) 4 7) 1
23. In which of the following octahedral 8) 2 9) 4 10) 1 11) 3 12) 3 13) 3 14) 2
complexes will the magnitude of ∆ 0 be the 15) 3 16) 4 17) 2 18) 3 19) 4 20) 4 21) 4
highest 22) 1 23) 1 24) 1 25) 1 26) 1 27) 4
3− 3−
1) Co (CN )6  2) Co (C2O4 )3 
LEVEL-III - HINTS
3+ 2. 3+ Primary valecy corresponds to oxidation
3) Co ( H 2O )6  4) Co ( NH 3 )6 
state and secondary valecy corresponds to
24. Which of the following is a correct Irving- coordination number primary=3, secondary=6.
Williams order? (Tendency of complex
formation) 3. Formula of complex is  MCl2 ( H 2O )4  Cl .
1) Mn 2 + < Fe 2 + < Co 2 + < Ni 2 + Ionisable Cl − atoms are only one.
2) Ni 2 + < Co 2 + < Fe 2 + < Mn 2 + M1V1 = M 2V2
3) Fe 2 + < Mn 2 + < Ni 2 + < Co 2 + 4. IV of four complexes
2+
4) Co < Mn < Fe < Ni 2+ 2+ 2+
(1) is 3, (2) is 2, (3) is 1, (4) is 0
25. Which order is correct in spectrochemical 6. are ambidentate ligands which
− NO2 − and − SCN
series of ligands? have two donor atoms.
1) Cl − < F − < C2O42− < NO2− < CN −
The complex [Co(en) 2 Cl2 ] shows geometrical
+
9.
2) CN − < C2O42− < Cl − < NO2− < F − as well as optical isomerism.

3) C2O42− < F − < Cl − < NO2− < CN − 15. µ = n ( n + 2 ) where n =5.

4) F − < Cl − < NO2− < CN − < C2O42− 17. For Mn +2 → n = 5

For Co +2 → n = 3
APPLICATION OF COMPLEXES IN
QUALITATIVE ANALYSIS AND METAL For Fe +2 → n = 4
CARBONYL COMPOUNDS AND STABILITY 18. For Fe +3 and Mn +2 → n = 5
OF CO-ORDINATION COMPOUNDS
26. Which of the following ligands is called π -
For Co +3 → n = 4
acceptors? For Cr +3 → n = 3
CO, CN − , NO + 19. Cl is weak field ligand and ( N − is strong field
(I ) ( II ) ( III ) ligand so, in [ NiCl4 ]
−2
hybridisation is sp3 in
1) I,II,III 2) I, II only −2
3) I,III only 4) III only  Ni (CN )4  hybridisation is dsp 2 .
 COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
Jr Chemistry E/M
PREVIOUS AIEEE QUESTIONS 2. Aqueous solution of Ni contains [ Ni ( H 2 O)6 ]2 +
2+

1. Which one of the following has an optical and its magnetic moment is 2.83 B.M. when
isomer [AIEEE-2010] ammonia is added in it, the predicted change
2+ 2+ in the magnetic moment of solution is :
1)  Zn (en )2 
 (
2)  Zn en ( NH 3 )  )2  1) It will remain same
3+ 3+
2) It increases from 2.83 B.M.
3) Co (en )3  4) Co ( H 2O )4 en  3) It decreases from 2.83 B.M.
4) It can not be predicted theoretically.
2. Which of the following facts about the 3. Which of the following complexes is a
complex Cr ( NH 3 )6  Cl3 is wrong. paramagnetic complex ?
[AIEEE-2011] 1) K 2  Ni (CN )4  2)  Ni ( H 2 O )6  ( NO3 ) 2

1) The complex innvolves d 2 sp3 hybridisation 3) [Co( NH 3 )6 ]Cl3 4) [ Pt ( NH 3 )4 ]Cl2

4. Which of the following are paramagnetic ?
and is octahedral shape
2) The complex is paramagnetic 1) K 4 [ Fe(CN )6 ] 2) K3 [Cr (CN )6 ]
3) The complex is an outer orbital complex 3) K3 [Co(CN )6 ] 4) K 2 [ Ni(CN )4 ]
4) The complex gives white precipitate which 5. Which of the following pairs of d-electron
silver nitrate solution. configuration exhibit both low and high spin
3. The magnetic moment (spin only) of tetrahedral complex
[ NiCl4 ]2− [AIEEE-2011] 1) d 1 , d 2 2) d 3 , d 4 3) d 7 , d 8 4) d 9 , d 10
1) 1.8BM 2) 5.86 BM 6. Assign the hybridisation, shape and magnetic
3) 2.82 BM 4) 3.82 BM moment of K 2 Cu (CN )4 
4. Which among the following will be named
1) sp 3 , tetrahedral, 1.73 BM
as dibromidobis (ethylene diamine)
chromium III bromide [AIEEE - 2012] 2) dsp 2 , square planar, 1.73 BM
+ − −
2) CrBr2 ( en )2 
3) sp 3 , tetrahedral, 2.8 BM
1) CrBr2 (en )2 
 
4) dsp 2 , square planar, 2.8 BM
+ +2
3) CrBr2 ( en ) 4) CrBr2 (en ) 7. Which of the following is most stable.
3+ 3−
5. Which of the following complex species is not 1)  Fe ( H 2O )6  2)  Fe (CN )6 
expected to exhibit optical isomerisim
3−
[MAINS-2013] 3)  Fe (C2O4 )3  4) [ FeCl6 ]3−
+
1) Co (en )2 Cl2  2) Co ( NH 3 )3 Cl3  COMPREHENSION TYPE QUESTIONS
+ 3+
Comprehension-1: Valence bond theory
3) Co (en ) ( NH 3 )2 Cl2  4) Co (en )3  successfully explains the magnetic behaviour of
complexes. The substances which contains
PREVIOUS AIEEE QUESTIONS - KEY unpaired electrons are paramagnetic and
1) 3 2) 3 3) 3 4) 1 5) 2 paramagnetic character increases as the number
of unpaired electrons increases. Magnetic
moment of a complex can be determined
LEVEL-IV experimentally and by using formula n(n + 2)
and we can determine the number of unpaired
1. Which is low spin complex ? electrons in it. This information is important in
1) [ Fe(CN )6 ]3− 2) [Co( NO2 )6 ]3− writing the electronic structure of complex
which in turn is also useful in deciding the
3) [Mn(CN )6 ]3− 4) All of these geometry of complex.
 JEE-MAIN-SR-CHEM-VOL-II COMPLEX COMPOUNDS
Jr Chemistry E/M
8. The magnetic moments (spin only) of [ NiCl4 ]2 − Comprehension-3: When degenerate
2−
d -orbitals of an isolated metal atom/ion come
and  Ni (CN )4  are: underinfluence of magnetic field of ligands,
1) 0, 0 2) 2.82 B.M., 2.82 B.M. the degeneracy is lost. Two sets of orbitals
3) 0, 2.82 B.M. 4) 2.82 B.M., 0 are obtained in case of octahedral and
9. There are four complexes of Ni. Select the tetrahedral complexes. The energy difference
complex/es which will be attracted by between these two set of orbitals is known as
magnetic field : crystal field splitting energy.
2− 15. The value of ∆ depends on
(I)  Ni (CN )4  (II) [ NiCl4 ]2 − 1) the nature of the metal cation
(III) Ni (CO )4 (IV)  Ni ( H 2 O )6 
2+ 2) nature of the ligands
3) geometry of the complex 4) all of these
1) I only 2) I and IV 16. The splitting power of the ligands in
3) II, III and IV 4) II and IV decreasing order is as follows :
10. The magnetic moments of complexes given
below are in the order : 1) CN − > NO2− > NH 3 > H 2O

(I) Ni (CO ) (II)  Mn (CN ) 

4−
2) CN − > NH 3 > NO2− > H 2O
4  6 
(III) [Cr ( NH 3 )6 ]
3+
(IV) [CoF6 ] 3− 3) NH 3 > CN − > NO2− > H 2O
1) I > II > III > IV 2) I < II < III < IV 4) H 2O > NH 3 > NO2− > CN −
3) IV > II > I > III 4) IV < II < I < III 17. Which of these species has same number of
11. The magnetic moment of [Cu ( NH 3 ) 4 ] was
2+
unpaired electrons with weak field as well as
found to be 1.73 B.M. The number of with strong field ligands.
unpaired electrons in the complex is : 1) Ti 2+ 2) Cr 3+ 3) Ni 2+ 4) all of these
1) 0 2) 1 3) 2 4) 3
LEVEL-IV - KEY
Comprehension - 2: When two or more
simple salts are mixed in storchiometric 1) 4 2) 1 3) 2 4) 2 5) 2 6) 2 7) 3
proportions and allowed to crystallised 8) 4 9) 4 10) 2 11) 2 12) 3 13) 4 14) 4
together, crystals of new compounds are 15) 4 16) 1 17) 4
formed. The new compound is known as
addition compound. LEVEL-IV - HINTS
12. The addition compound is a 5. d 3 and d 4 systems have e 2t12g and e 2t2g2
(high
1) double salt only
2) coordination compound only spin state) configuration. In weak field are e3t2g
0

3) either double salt or coordination compound

4) mixture of two salts and e 4t2g
0
(low spin state) configurations.
13. Mohr’s salt on dissociation in water gives 7. Complexes having more rings in structure will
1) positive test for Fe 2 + be more stable.
2) positive test for Fe 2+ and SO42 − 8. On the basis of VBT structure, [ NiCl4 ]2 − and
2−
3) positive test for Fe3+ , SO42 − and NH 4⊕ Ni (CN )4  have two and zero unpaired electrons

4) positive test for Fe 2+ , NH 4+ and SO42 − and magnetic moment is equal to n(n + 2) .
14. Complex compound is made up of 9. II and IV contain unpaired electrons.
1) simple cation and complex anion 10. The number of unpaired electrons in I, II, III &
2) complex cation and simple anion IV are 0, 1, 3 and 4 respectively.
3) complex cation and complex anion 11. The hybridisation is dsp 2 with one unpaired
4) all of these electron.