IIT JEE Coordination Compound Etoos DPP
IIT JEE Coordination Compound Etoos DPP
IIT JEE Coordination Compound Etoos DPP
Contents
Topic Page No.
Theory 01 - 12
Exercise - 1 13 - 24
Exercise - 2 25 - 32
Exercise - 3 33 - 38
Exercise - 4 39 - 40
Answer Key 41 - 49
Syllabus
IIT-JEE 2016
Coordination compounds: nomenclature of mononuclear coordination compounds, colour
(excluding the details of electronic transitions) and calculation of spin-only magnetic moment;
cis-trans and ionisation isomerisms, hybridization and geometries of mononuclear coordination
compounds (linear, tetrahedral, square planar and octahedral).
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COORDINATION COMPOUNDS
COORDINATION COMPOUNDS
Coordination Compounds : Those addition compounds which retain their identity
(i.e. doesn’t lose their identity) in solution are called coordination compounds. For example, when KCN
solution is added to Fe(CN)2 solution, the species formed when dissolved in water no longer gives tests
of Fe2+ and CN.
Fe(CN)2 + 4KCN Fe(CN)2 . 4KCN or K4 [Fe(CN)6] (aq.) 4K+ (aq.) + [Fe(CN)6]4– (aq.)
Coordination Number :
The coordination number of the central atom/ion is determined by the number of sigma bonds between
the ligands and the central atom/ions i.e. the number of ligand donor atoms to which the metal is directly
attached. Pi-bonds.
Cu+ 2, 4 Ni2+ 4, 6
Ag+ 2 Fe2+ 4, 6
Au+ 2, 4 Fe3+ 6
Hg22+ 2 Co2+ 4, 6
Cu2+ 4, 6 Co3+ 6
Ag2+ 4 Al 3+ 6
Pt 2+ 4 Sc 3+ 6
Pd2+ 4 Pt 4+ 6
Mg2+ 6 Pd4+ 6
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COORDINATION COMPOUNDS
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COORDINATION COMPOUNDS
2,4-pentanediono
acetylacetonato acac CH 3 COCHCOCH 3 –
or acetylacetonato
1,10-phenanthroline/
1,10-diaminophenanthrene phen,o-phen C 12H8 N2
phenanthroline
oxalato oxalato ox C 2 O 4 2–
1,2-ethanediylbis
1,2-bis(diphenylphophine)ethane dppe Ph 2P C2H4 PPh 2
(dipheylphosphene)
o-phenylenebis 1,2-phenylenebis
diars C 6 H4(As(CH3)2)2
(dimethylarsine) (dimethylarsene)
butanedienedioxime
dimethylglyoximato DMG HONC(CH 3 )C(CH 3)NO –
or dimethylglyoximato
O O
|| ||
1,2-ethanediyl —
O CH 2 C CH 2 CO —
:
|| CH 2 CO
||
—
O O
hydrotris-
pyrazolylborato
(pyrazo-1-yl)borato
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COORDINATION COMPOUNDS
Names of the anionic ligands end in –o. Anionic ligands ending with ‘ide’ are named by replacing ‘ide’
by suffix ‘ido’.
e.g . Symbol Name
N 3– Nitrido
Cl¯ Chlorido
O 22– Peroxido
Br¯ Bromido
O2H¯ Perhydroxido
CN¯ Cyanido
S 2– Sulphidido
O2– Oxido
NH2– Amidido
OH¯ Hydroxido
Ligands whose names end in ‘ite’ or ‘ate’ become ‘ito’ or ‘ato’ i.e., by replacing the ending ‘e’
with ‘o’ as follows
Symbol Name as ligand
CO32– Carbonato
C2O42– Oxalato
SO42– Sulphato
NO3¯ Nitrato
SO32– Sulphito
CH3COO¯ Acetato
NO2¯ (bonded through oxygen) nitrite (bonded through nitrogen) nitro
Neutral ligands are given the same names at the neutral molecules. For example. Ethylene diamine as
a ligand is named ethylene diamine in the complex. However some exceptions to this rule are
Aquo H2O
Ammine NH3
Carbonyl CO
Nitrosyl NO
Thiocarbonyl CS
tetraphosphorus P4
dioxygen O2
octasulphur S8
urea CO(NH2)2
2 sp [Ag(NH3)2]+
Linear [Ag(CN)2]¯
3 sp2 [Hg3]¯
4. sp3 [FeCl4]¯
[Ni(CO)4]0
Zn(NH3)4+2
[ZnCl4]–2,[CuX4]–2
where X = CN¯
Cl¯,Br¯, ¯, CNS
dsp2
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COORDINATION COMPOUNDS
dsp3 [CuCl5]–3
5. The d-orbital is [MoCl5]0
(n - 1)dz2 orbital [Fe(CO)5]0
sp3d
5. The d-orbital is ndx2–y2 [SbF 5]–2 IF 5
orbital
Square pyramidal
d2sp3
When d-orbitals are (n-1)
d-orbitals (Inner orbital [Cr(NH3)6+3]
6. complexes) or sp3d2 [Ti(H2O)6]+3
When d-orbitals are [Fe(CN)6]–2
nd orbital (Outer orbital [Co(NH3)6]+3
complexes) In both cases [PtCl6] –2[CoF 6] –3
p-orbitals are dz2 and dx2-y2
orbitals.
Octahedral
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COORDINATION COMPOUNDS
Crystal field splitting in octahedral coordination entities :
In general, ligands can be arranged in a series in the orders of increasing field strength as given below:
I– < Br– < SCN– < Cl– < S2– < F– < OH– < C2O42– < H2O < NCS– < edta4– < NH3 < en < NO2– <
CN– < CO
The two possibilites are :
(i) If 0 < P, the fourth electron enters one of the eg orbitals giving the configuration t32geg1. Ligands for
which 0 < P are known as weak field ligands and form high spin complexes.
(ii) If 0 > P, it becomes more energetically favourable for the fourth electron to occupy a t2g orbital with
configuration t2g4 eg0. Ligands which produce this effect are known as strong field ligands and form low
spin complexes.
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COORDINATION COMPOUNDS
Crystal field splitting in square planar coordination entities :
Relationship between the wavelength of light absorbed and the colour observed In some coordination entitles
Table
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Coordination entity Wavelength of light Colour of light Colour of coordination
absorbed (nm) absorbed entity
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
[CoCl(HN3)5]2+ 535 Yellow Violet
ISOMERISM :
STRUCTURAL ISOMERISM :
(A) Ionisation isomerism :
This type of isomerism occurs when the counter ion in a coordination compound is itself a potential ligand
and can displace a ligand which can then become the counter ion. For example, following complexes
show ionisation isomerism.
[Co(NH3)5SO4]NO3 and [Co(NH3)5NO3]SO4
[Co(NH3)4(NO2)Cl]Cl and [Co(NH3)4Cl2]NO2.
[Co(NH3)4(H2O)Cl]Br2 and [Co(NH3)4BrCl]Br.H2O. [Also an example of hydrate isomers.]
[Pt(NH3)4Cl2]Br2, and [Pt(NH3)4Br2]Cl2.
[CoCl(en)2(NO2)]SCN, [Co(en)2(NO2)SCN]Cl and [Co(en)2(SCN)Cl]NO2
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COORDINATION COMPOUNDS
Stereoisomerism
Geometrical Isomerism
This type of isomerism arises in heteroleptic complexes due to different possible geometric arrangements
of the ligands. Geometrical isomerism is common among coordination compounds with coordination numbers
4 and 6.
Coordination Number Four :
Tetrahedral Complex :
The tetrahedral compounds can not show geometrical isomerism as we all know that all four positions
are equivalent in tetrahedral geometry.
Square Planar Complex :
In a square planar complex of formula [Ma2b2] [a and b are unidentate], the two ligands ‘a’ may be arranged
adjacent to each other in a cis isomer, or opposite to each other in a trans isomer as depicted.
Optical Isomerism :
A coordination compound which can rotate the plane of polarised light is said to be optically active.
When the coordination compounds have same formula but differ in their ability to rotate directions
of the plane of polarised light are said to exhibit optical isomerism and the molecules are optical
isomers. Optical isomers are mirror images that cannot be superimposed on one another. These are
called as enantiomers.
Octahedral complex :
Optical isomerism is common in octahedral complexes involving didentate ligands. For example,
[Co(en) 3] 3+ has d and forms as given below.
d and of [Co(en) 3 ] 3+
Cis-isomer of [PtCl2(en)2 ]2+
show optical isomerism as shown below because of the absence of plane
of symmetry as well as centre of symmetry.
Tetrahedral complex :
Optical isomerism is expected in tetrahedral complexes of the type [Mabcd] analogous to tetrahedral
carbon atom.
Organometallic compounds :
Bonding in Metal Carbonyls
The metal–carbon bond in metal carbonyls possess both s and p character. The M—C bond is formed
by the donation of lone pair of electrons on the carbonyl carbon (CO is a weak base) into a vacant orbital
of the metal. The M — C bond is formed by the donation of a pair of electrons from a filled d orbital
of metal into the vacant antibonding * orbital of carbon monoxide. Thus carbon monoxide acts as donor
(OC M) and a acceptor (OC M), with the two interactions creating a synergic effect which strengthens
the bond between CO and the metal as shown in figure.
M C O
Synergic bonding
(i) As M — C bonding increases, the C — O bond becomes weaken. The greater the positive charge
on the central metal atom, the less readily the metal can donate electron density into the * orbitals of
the carbon monoxide ligands to weaken the C — O bond.
(ii) In contrast, in the anionic complex (i.e. carbonylate anion) the metal has a greater electron density
to be dispersed, with the result that M — C bonding is enhanced and the C — O bond is diminished
in strength. For example ; in isoelectronic complexes the strength of metal-ligand bond increases and
strength of C — O bond in CO decreases (because bond order decreases) as the negative charge on
the complexes increases.
Thus order of CO bond strengths ;
(a) [M(CO)6]+ > [Cr(CO)6] > [V(CO)6]– > [Ti(CO)6]2–. (b) [Ni(CO)4] > [Co(CO)4]– > [Fe(CO)4]2–.
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COORDINATION COMPOUNDS
(a) en (p)
(d) gly
(e) ox (s)
(t)
(a) (b) (c) (d) (e) (a) (b) (c) (d) (e)
(A) r p t q s (B) r p t q s
(C) p s q r t (D) s q t p r
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COORDINATION COMPOUNDS
B-7. K3[Fe(CN)6] is –
(a) Potassium hexacynoferrous(III) (b) Potassium hexacynoferrate(III)
(c) Potassium ferricyanide (d) Hexacyano ferrate(III) potassium
Correct answer is –
(A) Only (a) and (b) (B) Only (b) and (c) (C) Only (a) and (c) (D) Only (b) and (d)
B-10. A complex anion is formed by Osmium (in some oxidation state) with ligands (in proper number so that coordination
number of osmium becomes six). Which of the following can be its correct IUPAC name?
(A) pentachloridonitridoosmium(VI) (B) pentachloridonitridoosmate(VI)
(C) azidopentachloridoosmate(VI) (D) None of these
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COORDINATION COMPOUNDS
B-11. Complex ion [ FeN3(O2)(SCN)4]4 – is named as : (coordination number of central metal ion in complex is six)
(A) azidosuperoxidotetrathiocyanato-S-ferrate(II) (B) azidodioxygentetrathiocyanatoferrate(III)
(C) azidoperoxidotetrathiocyanato-S-ferrate(II) (D) azidodioxidotetrathiocyanato-S-ferrate(III)
B-14. A complex cation is formed by Pt (in some oxidation state) with ligands (in proper number so that coordination
number of Pt becomes six). Which of the following can be its correct IUPAC name :
(A) Diammineethylenediaminedithiocyanato-S-platinum (II) ion
(B) Diammineethylenediaminedithiocyanato-S-platinate (IV) ion
(C) Diammineethylenediaminedithiocyanato-S-platinum (IV) ion
(D) Diamminebis (ethylenediamine) dithiocyanate-S- platinum (IV) ion
C-1. When AgNO3 is added to a solution of Co(NH3)5Cl3, the precipitate of AgCl shows two ionisable chloride
ions. This means that-
(A) two chlorine atom satisfy primary valency and one secondary valency.
(B) one chlorine atom satisfies primary as well as secondary valency.
(C) three chlorine atoms satisfy primary valency.
(D) three chlorine atoms satisfy secondary valency.
C-2. A co-ordination complex of cobalt has molecular formula containing five ammonia molecules, one nitro group
and two chlorine atoms for one cobalt atom. One mole of this compound produces three mole ions in an
aqueous solution. In reacting this solution with excess of silver nitrate solution, two moles of AgCl get precipitated.
The ionic formula of this complex would be –
(A) [(Co(NH3)4.NO2Cl].[(NH3)Cl] (B) [(Co(NH3)5Cl].[Cl(NO2)]
(C) [(Co(NH3)5(NO2)]Cl2 (D) [(Co(NH3)5].[(NO2)2Cl2]
C-3. Which of the following complex will give white precipitate with barium chloride solution ?
(A) [Cr(NH3)5Cl]SO4 (B) [Cr(NH3)SO4]Cl (C) [Co(NH3)6]Br3 (D) None of these
C-4. Give the correct increasing order of electrical conductivity of aqueous solutions of following complex entities.
I. [Pt(NH3)6]Cl4 II. [Cr(NH3)6]Cl3 III. [Co(NH3)4Cl2]Cl IV. K2[PtCl6]
(A) III < IV < II < I (B) IV < II < III < I (C) II < I < IV < III (D) I < II < IV < III
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COORDINATION COMPOUNDS
C-7. A compound is made by mixing cobalt(III) nitrite and potassium nitrite solutions in the ratio of 1 : 3. The aqueous
solution of the compound showed 4 particles per molecule whereas molar conductivity reveals the presence of
six electrical charges. The formula of the compound is :
(A) Co(NO2)3 . 2KNO2 (B) Co(NO2)3 . 3KNO2 (C) K3[Co(NO2)6] (D) K[Co(NO2)4]
C-9. A co-ordination complex has the formula PtCl4.2KCl. Electrical conductance measurements indicate the presence
of three ion in one formula unit. Treatment with AgNO3 produces no precipitate of AgCl. What is the co-ordination
number of Pt in this complex ?
(A) 5 (B) 6 (C) 4 (D) 3
C-11. How many moles of AgCl would be obtained, when 100 ml of 0.1 M Co(NH3)5Cl3 is treated with excess of
AgNO3?
(A) 0.01 (B) 0.02 (C) 0.03 (D) none of these
C-13. On adding AgNO3 solution to a solution of [Pt(NH3)3Cl3]Cl, the percentage of total chloride ion precipitated is:
(A) 100 (B) 75 (C) 50 (D) 25
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COORDINATION COMPOUNDS
D-2. Match the geometry given in column A with the complex given in column B using the codes given below :
Column (A) Column (B)
i) Tetrahedral (a) [Cu(NH3)4]2+
ii) Octahedral (b) [Ag(NH3)2]+
iii) Square planar (c) Fe(CO)5
iv) Trigonal bipyramidal (d) [Cr(H2O)6]3+
v) Linear (e) [NiCl4]2–
(A) (i)-(e), (ii)-(d), (iii)-(a), (iv)-(c) ,(v)-(b) (B) (i)-(d), (ii)-(e), (iii)-(a), (iv)-(c) ,(v)-(b)
(C) (i)-(d), (ii)-(e), (iii)-(b), (iv)-(a) ,(v)-(c) (D) (i)-(c), (ii)-(e), (iii)-(b), (iv)-(a) ,(v)-(d)
E-4. The crystal field splitting energy for octahedral complex (o) and that for tetrahedral complex (t ) are related as:
4 9
(A) t = (B) t = 0.5 o (C) t = 0.33 o (D) t =
9 0 4 0
E-6. What is the shape of Fe(CO)5 molecule ? Given that its dipole moment = 0.
(A) Tetrahedral (B) Octahedral (C) Trigonal bipyramidal (D) Square pyramidal
E-9. Which of the following complexes has a geometry different from others ?
(A) [Ni Cl4]2– (B) Ni (CO)4 (C) [Ni(CN)4]2– (D) [Zn(NH3)4]2+
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COORDINATION COMPOUNDS
F-2. From the stability constant (hypothetical values), given below, predict which is the most stable complex ?
(A) Cu2+ + 4NH3 [Cu(NH3)4]2+ , K = 4.5 × 1011
(B) Cu2+ 4CN– [Cu(CN)4]2–, K = 2.0 × 1027
(C) Cu2+ + 2en [Cu(en)2]2+ , K = 3.0 × 1015
2+
(D) Cu + 4H2O [Cu(H2O)4] , 2+ K = 9.5 × 108
G-3. Which one of the following octahedral complexes will not show geometrical isomerism
(A and B are monodentate ligands) ?
(A) [MA5B] (B) [MA2B4] (C) [MA3B3] (D) [MA4B2]
G-4. cis-trans-isomerism is found in square planar complexes of the molecular formula (a and b are monodentate
ligands) –
(A) Ma4 (B) Ma3b (C) Ma2b2 (D) Mab3
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COORDINATION COMPOUNDS
G-6. [Co(NH3)5Br] SO4 and [Co(NH3)5SO4] Br are...................... isomers.
(A) Linkage (B) Geometrical (C) Ionization (D) Optical
CH2 CH2
H2N H2N
en M en M
A
A en
(A) geometrical isomers (B) position isomers
(C) optical isomers (D) identical
G-12. Theoretically the number of geometrical isomers expected for octahedral complex [Mabcdef] is :
(A) Zero (B) 30 (C) 15 (D) 9
G-14. Which of the following complexes show geometrical as well as optical isomerism ?
(1) [Cr(OX)3]3– (2) [Rh(en)2Cl2]+ (3) [Co(NH3)2(Cl)2(en)]+
(A) 1 only (B) 1 and 2 only (C) 2 and 3 only (D) All 1, 2, 3
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COORDINATION COMPOUNDS
H-3. In which of the following pair the EAN of central metal atom is same?
(A) [Fe(CN)6]3– and [Fe(CN)6]4– (B) [Cr(NH3)6]3+ and [Cr(CN)6]3–
3– 4–
(C) [FeF6] and [Fe(CN)6] (D) [Ni(CO)4] and [Ni(CN)4]2–
H-4. EAN of a metal carbonyl M(CO)x is 36. If atomic number of metal M is 26, what is the value of x ?
(A) 4 (B) 8 (C) 5 (D) 6
I-6. What is wrong about the compound K [Pt (2 – C2H4) Cl3] ?
(A) It is called Zeise's salt. (B) It is bonded complex.
(C) Oxidation number of Pt is +4. (D) Four ligands surround the platinum atom.
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COORDINATION COMPOUNDS
1. The value of crystal field splitting (0) for [Ti(H2O)6]3+ is 243 kJ mol–1. The crystal field stabilization energy
(CFSE) in this complex is : (in kJ mol–1).
3 2 2
(A) × 243 (B) × 243 (C) 3 × × 243 (D) 243
5 5 5
3. The heat of hydration of Cr2+ ion is 460 k cal/mole. For [Cr(H2O)6]2+, 0 = 13,900 cm–1. What heat of hydration
would be, if there were no crystal field stabilisation energy ?
(A) – 436 k cal/mole (B) – 245 k cal/mole (C) – 4.84 k cal/mole (D) none of these
Comprehension # 2
In metal carbonyls , there is synergic bonding interaction between metal and carbon monoxide .This leads to
increase in strength of metal ligand bond and decrease in bond order of CO in carbonyl complex as compared
to bond order in carbon monoxide.
Simple carbonyls are invariably spin-paired complexes except for vanadium metal.
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COORDINATION COMPOUNDS
6. Which amongst the following metal carbonyls are inner orbital complexes with diamagnetic property ?
(I ) Ni(CO)4; (II ) Fe(CO)5 ; (III ) V(CO)6 (IV) Cr(CO)6
Select the correct answer from the codes gives below :
(A) I and II only (B) II , III and IV only (C) II and IV only (D) I ,II and IV only
7. Which one of the following metal carbonyls involves the d2sp3 hybridisation for the formation of metal-carbon
bonds and is paramagnetic ?
(A) [Cr(CO)6] (B) [ V(CO)6 ] (C) [ Mo(CO)6 ] (D) [W(CO)6 ]
(A) (NH4)2[NiCl4] and (NH4)2[Ni(CN)4] (p) Both show same electrical conductance.
(B) CoCl3.6NH3 and PtCl4.5NH3 (q) Both show same effective atomic number.
(C) [Pt(NH3)2Cl2] and (NH4)2[PtCl4] (r) Both show same primary valencies.
(D) K2[Fe(H2O)6] and K4[FeCl6] (s) Both gives white participate with AgNO3 solution.
10. Match the complexes given in column-I with their characteristic(s) given in column-II.
Column – I Column – II
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COORDINATION COMPOUNDS
ASSERTION / REASONING
DIRECTIONS :
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
12. Statement-1 : In the co-ordination complex [Pt(NH3)4 Cl2] Br2, a yellow precipitate of AgBr is obtained on
treating it with AgNO3.
Statement-2 : Bromide ions are present as counter ions in the ionization sphere.
13. Statement-1 : In the complex [Co(NH3)3 Cl3], chloride ions satisfy the primary valencies as well as the secondary
valencies of cobalt metal.
Statement-2 : [Co(NH3)3Cl3] shows geometrical as well as optical isomerism.
14. Statement-1 : All the complexes of Pt (+II) and Au(+ III) with strong field as well as with weak field ligands are
square planar.
Statement-2 : The crystal field splitting o is larger for second and third row transition elements , and for more
highly charged species. This larger value of 0 energetically favours the pairing of electron for square planar
geometry.
15. Statement-1 : The value of o for M3+ complexes are always much higher than value for M2+ complexes (for the
same set of ligands)
Statement-2 : The crystal field stabilization energy of [Co(NH3)6]3+ < [Rh(NH3)6]3+
16. Statement-1 : The complex [Cr(SCN)(NH3)5 ]Cl2 is linkage isomeric with [Cr(NCS)(NH3)5 ]Cl2.
Statement-2 : SCN– is an ambident ligand in which there are two possible coordination sites.
17. Statement-1 : The [Ni(en)3] Cl2 has higher stability than [Ni(NH3)6] Cl2
Statement-2 : In [Ni(en)3] Cl2, the geometry of Ni is octahedral.
19. Statement-1 : In the reaction [CoCl2(NH3)4]+ + Cl– [CoCl3(NH3)3] + NH3, when reactant is in cis-form two
isomers of the product are obtained.
Statement-2 : Third chloride ion replaces an ammonia cis to both chloride ion or trans to one of the chloride ion.
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4– 2–
20. Statement-1 : [NiF6] and [NiF6] both are high spin complexes.
Statement-2 : F– is a weak field ligand.
21. Statement-1 : The correct order for the wave length of absorption in the visible region is ;
[Ni(NO2)6]4 – < [Ni(NH3)6]2+ < [Ni(H2O)6]2+
Statement-2 : The stability of different complexes depends on the strength of the ligand field of the various
ligands.
TRUE / FALSE
24. The 'spin only' magnetic movement of an octahedral complex having CFSE = – 0.6 0 and surrounded by weak
field ligands can be 4.9 BM or 1.73 BM
25. [Cr(C2O4)3]3– and [Cr(NH3)2Cl2(en)]+ both show cis-trans as well as optical isomerism.
27. Sodium nitroprusside has iron in + II oxidation state and the complex is diamagnetic in nature.
32. The complex [Cr(H2O)6]Cl3 loses six water molecules to conc. H2SO4 and does not give any precipitate with
AgNO3.
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4. What is the oxidation number of chromium in the dimeric hydroxo bridged species ?
H 4+
O
(H2O)4 Cr Cr(H2O)4
O
H
(A) + 6 (B) + 4 (C) + 3 (D) + 2
1
6. Which of the following is most likely formula of platinum complex, if of total chlorine of the compound is
4
precipitated by adding AgNO3 to its aqueous solution ?
(A) PtCl4.6H2O (B) PtCl4.5H2O (C) PtCl4.2H2O (D) PtCl4.3H2O
7. 50 ml of 0.2 M solution of a compound with empirical formula CoCl3.4NH3 on treatment with excess of AgNO3(aq)
yields 1.435 g of AgCl. Ammonia is not removed by treatment with concentrated H2SO4. The formula of the
compound is :
(A) Co(NH3)4Cl3 (B) [Co(NH3)4Cl2]Cl (C) [Co(NH3)4Cl3 (D) [CoCl3(NH3)]NH3
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9. How many moles of AgCl would be obtained, when 100 ml of 0.1 M Co(NH3)5Cl3 is treated with excess of
AgNO3?
(A) 0.01 (B) 0.02 (C) 0.03 (D) none of these
12. Which of the following complex is not correctly matched with its geometry ?
(A) [NiCl2(Ph3P)2] – tetrahedral (B) [Co(Py)4]2+ – square planar.
3–
(C) [Cu(CN)4] – tetrahedral (D) [Fe(CO)4]2– – square planar.
13. Match Column-I with Column-II and select the correct answer with respect to hybridisation using the codes given
below :
Column - I Column - II
(Complex) (Hybridisation)
(I) [Au F4]– (p) dsp2 hybridisation
(II) [Cu(CN)4]3– (q) sp3 hybridisation
(III) [Co(C2O4)3] 3– (r) sp3d2 hybridisation
(IV) [Fe(H2O)5NO] 2+ (s) d2sp3 hybridisation
Codes :
(I) (II) (III) (IV) (I) (II) (III) (IV)
(A) q p r s (B) p q s r
(C) p q r s (D) q p s r
14. All the metal ions contains t2g6 eg0 configurations. Which of the following complex will be paramagnetic?
(A) [FeCl(CN)4(O2)]4- (B) K4[Fe(CN)6] (C) [Co(NH3)6]Cl3 (D) [Fe(CN)5(O2)]-5
15. The complex [ Fe (H2O)5 NO+ ]2+ is formed in the ‘brown ring test’ for nitrates. Choose the incorrect statement
for the complex.
(A) Its magnetic moment is approximately 3.9 B.M.
(B) The oxidation state of iron is + 1
(C) The hybridisation of central metal ion is sp3 d2
(D) The brown colour of the ring is due to d – d transition.
16. Which one of the following statement is false for nickel-dimethylglyoximate complex ?
(A) The stability of complex is only due to the presence of intra-molecular hydrogen bonding.
(B) The complex is stable because tridentate dimethyl glyoxime ligand forms a five membered chelate rings.
(C) The complex is stable as it has five membered chelate rings as well as intra molecular hydrogen bonding.
(D) A and B both.
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17. Which of the following statements are correct for the complex [Co(NH3)4(Cl) (NO2)]Cl ?
1. Cobalt is in + 3 oxidation state involving d2sp3 hybridisation.
2. Cobalt is in + 3 oxidation state involving sp3d2 hybridisation.
3. It shows ionisation as well as linkage isomerism.
4. It also shows geometrical isomerism.
(A) 1, 3 and 4 only (B) 2, 3 and 4 only (C) 1 and 4 only (D) 2 and 4 only.
21. Which of the following complex does not show geometrical isomerism ?
(A) [ Co (NH3)4 Cl2 ]+ (B) [ Co (NH3)3 (NO2)3 ] (C) [ Cr (en)3 ]3+ (D) [ Pt (gly)2]
22. [Fe(en)2(H2O)2]2+ + en complex(X). The correct statement about the complex (X) is :
(A) it is a low spin complex. (B) it is diamagnetic.
(C) it shows geometrical isomerism. (D) (A) and (B) both.
and
24. The total number of possible isomers of the compound [CuII(NH3)4] [PtIICl4] are:
(A) 3 (B) 5 (C) 4 (D) 6
25. On treatment of [Pt(NH3)4]2+ with concentrated HCl, two compounds (I) and (II) having the same formula,
[Pt(NH3)2Cl2] are obtained, (I) can be converted into (II) by boiling with dilute HCl. A solution of (I) reacts with
oxalic acid to form [Pt(NH3)2(C2O4)] whereas (II) does not react. Point out the correct statement of the following.
(A) (I) cis, (II) trans; both tetrahedral (B) (I) cis, (II) trans; both square planar
(C) (I) trans, (II) cis; both tetrahedral (D) (I) trans, (II) cis; both square planar
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27. The complex ion has two optical isomers. Their correct configurations are :
(A) (B)
(C) (D)
28. Of the following complex ions, the one that probably has the largest overall formation constant, Kf, is :
(A) [Co(NH3)6]3+ (B) [Co(H2O)6]3+ (C) [Co(NH3)2(H2O)4]3+ (D) [Co(en)3]3+
29. What is the ratio of uncomplexed to complexed Zn2+ ion in a solution that is 10 M in NH3, if the stability constant
of [Zn(NH3)4]2+ is 3 × 109 ?
(A) 3.3 × 10–9 (B) 3.3 × 10–11 (C) 3.3 × 10–14 (D) 3 × 10–13
35. Which of the following statements is/are incorrect for the complex [Cr(H2O)6]Cl3 ?
(A) It has a magnetic moment of 3.83 BM.
(B) The distribution of 3d electrons is 3dxy1, 3dyz1, 3dzx1
(C) The ligand has satisfied both primary and secondary valencies of chromium.
(D) It shows ionization as well as hydrate isomerism.
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37. Which of the following statements is/are true for the complexes, [Fe(H2O)6]2+ , [Fe(CN)6]4– , [Fe(C2O4)3]3–
and [Fe(CO)5] ?
(A) Only [Fe(C2O4)3]3– show optical isomerism.
(B) [Fe(C2O4)3]3– is less stable than [Fe(CN)6]2–
(C) All complexes have same effective atomic number.
(D) [Fe(CO)5] shows back bonding.
39. In which of the following complexes more than one type of structural isomerism is possible ?
(A) [Co(NH3)5 (NO2)]Cl (B) [Co(NH3)5(H2O)](NO2)3
(C) [Pt(NH3)4][Pt(SCN)4] (D) [Cr(NH3)4 (NO2)2] (NO3)2
1. Name the following compounds(All these are important compounds, will be used in different fields of chemistry)
(c) [Fe(CO)5], A highly toxic volatile liquid.
(d) [Fe(C2O4)3]3–, The ion formed when Fe2O3 rust is dissolved in oxalic acid, H2C2O4.
(e) [Cu(NH3)4]SO4, A deep blue compound obtained when CuSO4 is treated with excess of NH3.
(f) Na[Cr(OH)4], The compound formed when Cr(OH)3 precipitate is dissolved in excess of NaOH.
(g) Co(gly)3, A complex that contains the anion of amino acid, glycine.
(h) [Fe(H2O)5(SCN)]2+, The red complex ion formed in the qualitative analysis test of Fe3+ ion.
(i) K2[HgI4], Alkaline solution of this complex is called Nessler’s Reagent.
(j) Co[Hg(SCN)4], Deep blue crystalline precipitate obtained in qualitative detection of Hg2+.
(k) Fe4[Fe(CN)6]3, Prussian blue, deep blue colored complex obtained in detection of Fe2+.
(l) K3[Co(NO2)6], Potassium cobaltinitrite or Fischer salt yellow precipitate obtained in detection of
Co2+.
(m) [Ni(dmg)2], Rosy red precipitate obtained in detection of Ni2+ ions.
(n) K2[PtCl6], Yellow precipitate obtained in detection of potassium ions(similar complex is formed
with NH4+ ions also).
(o) Na2[Fe(CN)5NO+], Sodium nitroprusside used for detection of sulphide ions/sulphur.
(p) [Fe(H2O)5(NO+)]SO4, Brown ring complex, obtained in detection of Fe2+ ions.
(q) [Cu(CN)4]3–, Colourless stable soluble complex obtained in detection of Cu2+ on adding excess of
KCN solution.
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CN = 6
(j) [Mn(CN)6]3– ---------------------- ----------------------
2 ----------------------
5. (A), (B) and (C) are three complexes of chromium(III) with the empirical formula H12O6Cl3Cr. All the three complexes
have water or chloride ion as ligands. Complex (A) does not react with concentrated H2SO4, whereas complexes
(B) and (C) lose 6.75% and 13.5% of their original weight, respectively, on treatment with concentrated H2SO4.
(i) Identify (A), (B) and (C) (ii) Write their formulae
(iii) Calculate their EAN. (iv) By the addition of AgNO3 what happens with each complex.
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6. A metal complex having composition Cr(NH3)4Cl2Br has been isolated in two forms A and B. The form A reacts
with AgNO3 to give a white precipitate readily soluble in dilute aqueous ammonia, whereas B gives a yellow
precipitate soluble in concentrated ammonia.
(i) Write the formulae of A and B.
(ii) State hybridisation of chromium in each.
(iii) Calculate their magnetic moments for each (spin-only value).
(iv) Calculate the EAN for both.
(v) Will they conduct electricity or not.
(vi) Write the formula of the complexes formed when the precipitates dissolve in aqueous ammonia & the
concentrated ammonia respectively.
7. (a) Which of the complexes (a) [Cr(edta)]–, (b) [Ru(en)3]2+ and (c) [Pt(dien)Cl]+ are chiral ?
(b) Give the IUPAC name of the complex, [IrH(CO) (PMe3)2] and also give the hybridisation of the central atom
along with the magnetic moment.
8. Draw all the possible isomers of [Co (NH3)2 (en) Cl2 ]+.
9. (a) Draw all possible constitutional isomers of the compound Ru(NH3)5(NO2)Cl. Label the isomers as linkage
isomers or ionization isomers.
(b) There are six possible isomers for a square planar palladium(II) complex that contains two Cl– and two SCN–
ligands. Sketch the structures of all six, and label them according to the classification.
10. Tell how many diastereoisomers are possible for each of the following complexes, and draw their structures.
(a) [Cr(NH3)2Cl4]– (b) [Co(NH3)5Br]2+ (c)[FeCl2(NCS)2]2–
2–
(d) [PtBr2Cl2] (e) [Co(en)(SCN)4] –
(f) [Cr(NH3)2(H2O)2Cl2]+ (g) [Ru(NH3)3I3]
11. Which of the following complexes can exist as enantiomers? Draw their structures.
(a) cis-[Co(NH3)4Br2]+ (b) cis-[Cr(H2O)2(en)2]3+ (c) [Cr(gly)3]
(d) [Cr(en)3]3+ (e) cis-[Co(NH3)Cl(en)2]2+ (f) trans-[Co(NH3)2(en)2]2+
12. Predict the number of unpaired electrons in a tetrahedral d6 ion and in a square planar d7 ion.
Note : If answer in 1 and 2 represent as 12.
13. From Meridional and facial isomer of [Ma 3b3 ]n on replacement of only one 'a' by 'b', the number of isomer of
the product obtained are ______ and _______ respectively.
[If answer is 2 and 5 represent as 25]
14. In how many of the following entities the central metal ions have the oxidation state of + 2 ?
(a) [NiBr4]2– (b) [Fe(CN)6]3– (c) [MnBr4]2– (d) [AuCl4]–
(e) [Fe(H2O)6]2+ (f) [Pt(NH3)4]2+ (g) [Co(SCN)4]2–
15. In Hx[Pt y6], y is monodentate negatively charged ligand then find out the value of x.
16. The total number of possible coordination isomer for the given compound is [Pt(NH3)4Cl2][PtCl4].
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20. How many of the following cases, EAN rule will be followed ?
K4[Fe(CN)6] [Fe(NH3)6]3+ V(CO)6
23. Number of (n – 1) d orbitals involved in the hybridisation of central metal ion in brown ring complex,
[Fe(H2O)5NO+]SO4 is :
24. How many of the following statements are correct for Nickel carbonyl [Ni(CO)4] ?
(i) It is a colourless compound.
(ii) The Ni — C— O group is linear.
(iii) The four carbonyl group are lying at the corners of a regular tetrahedron.
(iv) The metal – carbon bond length (for bond) does not alter.
(v) There is synergic interaction between nickel metal and ligand CO.
(vi) The oxidation state of nickel is zero.
(vii) The effective atomic number (EAN) of nickel atom is 34.
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2. The complex ion which has no 'd' electrons in the central metal atom is : [JEE–2001, 1/35]
[Atomic number Cr = 24, Mn = 25, Fe = 26, Co = 27]
(A) [MnO4]¯ (B) [Co(NH3)6]3+ (C) [Fe(CN)6]3– (D) [Cr(H2O)6]3+
3. A metal complex having composition Cr(NH3)4 Cl2Br has been isolated in two forms A and B. The form A reacts
with AgNO3 to give a white precipitate readily soluble in dilute aqueous ammonia, where as B gives a pale yellow
precipitate soluble in concentrated ammonia. Write the formula of A and B and state the hybridization of chromium
in each. Calculate their magnetic moments (spin only value). [JEE–2001, 5/100]
4. Deduce the structure of [NiCl4]2– and [Ni(CN)4]2– considering the hybridisation of the metal ion. Calculate the
magnetic moment (spin only) of the species. [JEE–2002, 5/60]
5. A green complex, K2[Cr(NO)(NH3)(CN)4] is paramagnetic and has eff = 1.73 BM. Write the IUPAC name of the
complex and draw the structure of anion and find out the hybridisation of metal ion. [JEE–2003, 4/60]
7. The spin magnetic moment of cobalt in the compound, Hg [Co(SCN)4] is : [JEE–2004, 3/84]
(A) 3 (B) 8 (C) 15 (D) 24
8. When dimethyl glyoxime is added to the aqueous solution of nickel (II) chloride in presence of dilute ammonia
solution, a bright red coloured precipitate is obtained. [JEE–2004, 4/60]
(a) Draw the structure of bright red substance.
(b) Write the oxidation state of nickel in the substance and hybridisation.
(c) State whether the substance is paramagnetic or diamagnetic.
11. The bond length in CO is 1.128 Å. What will be the bond length of CO in Fe(CO)5 ? [JEE–2006, 5/184]
(A) 1.158 Å (B) 1.128 Å (C) 1.178 Å (D) 1.118 Å
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Comprehension # (Q.12 to Q.14)
NiCl2 KCN
complex A
HCN
KCl
NiCl2
complex B
excess
A & B complexes have the co-ordination number 4.
12. The IUPAC name of complexes ‘A’ & ‘B’ are respectively : [JEE–2006, 5/184]
(A) Potassium tetracyanonickelate() and Potassium tetrachloronickelate()
(B) Potassium tetracyanonickel() and Potassium tetrachloronickel()
(C) Potassium cyanonickelate() and Potassium chloronickelate()
(D) Potassium cyanonickel() and Potassium chloronickel()
14. What are the magnetic nature of ‘A’ & ‘B’ ? [JEE–2006, 5/184]
(A) Both diamagnetic.
(B) ‘A’ is diamagnetic & ‘B’ is paramagnetic with one unpaired electrons.
(C) ‘A’ is diamagnetic & ‘B’ is paramagnetic with two unpaired electrons.
(D) Both are paramagnetic.
15. Among the following metal carbonyls, the C – O bond order is lowest in : [JEE–2007, 3/162]
(A) [Mn(CO)6]+ (B) [V(CO)6]¯ (C) [Cr(CO)6)] (D) [Fe(CO)5]
16. Match the complexes in Column-I with their properties listed in Column-II. [JEE–2007, 6/162]
Column-I Column-II
(A) [Co(NH3)4(H2O)2]Cl2 (p) Geometrical isomers
(B) [Pt(NH3)2Cl2] (q) Paramagnetic
(C) [Co(H2O)5Cl]Cl (r) Diamagnetic
(D) [Ni(H2O)6]Cl2 (s) Metal ion with +2 oxidation state
18. Both [Ni(CO)4] and [Ni(CN)4]2– are diamagnetic. The hybridisation of nickel in these complexes, respectively, are :
[JEE–2008, 3/163]
3 3 3 2 2 3
(A) sp , sp (B) sp , dsp (C) dsp , sp (D) dsp , sp2
2
19. Statement - 1 : The geometrical isomers of the complex [M(NH3)4Cl2] are optically inactive, and
Statement - 2 : Both geometrical isomers of the complex [M(NH3)4Cl2] possess axis of symmetry.
[JEE–2008, 3/163]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
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21. The compound(s) that exhibit(s) geometrical isomerism is(are) : [JEE–2009, 4/160]
(A) [Pt(en)Cl2] (B) [Pt(en)2]Cl2 (C) [Pt(en)2Cl2]Cl2 (D) [Pt(NH3)2Cl2]
22. The spin only magnetic moment value (in Bohr magneton units) of Cr(CO)6 is : [JEE–2009, 3/160]
(A) 0 (B) 2.84 (C) 4.90 (D) 5.92
(A)
(B)
(C)
(D)
25. The complex showing a spin-only magnetic moment of 2.82 B.M. is : [JEE–2010, 5/163]
(A) Ni(CO)4 (B) [NiCl4]2– (C) Ni(PPh3)4 (D) [Ni(CN)4]2–
26. Total number of geometrical isomers for the complex [RhCl(CO)(PPh3)(NH3)] is : [JEE–2010, 3/163]
27. Geometrical shapes of the complexes formed by the reaction Ni2+ with Cl–, CN– and H2O, respectively, are :
[JEE–2011, 3/240]
(A) octahedral, tetrahedral and square planar (B) tetrahedral, square planar and octahedral
(C) square planar, tetrahedral and octahedral (D) octahedral square planar and octahedral
29. The colour of light absorbed by an aqueous solution of CuSO4 is : [JEE–2012, 3/210]
(A) orange-red (B) blue-green (C) yellow (D) violet
30. As per IUPAC nomenclature, the name of the complex [Co(H2O)4 (NH3)2]Cl2 is : [JEE-2012, 3/210]
(A) Tetraaquadiaminecobalt (III) chloride (B) Tetraaquadiamminecobalt (III) chloride
(C) Diaminetetraaquacobalt (III) chloride (D) Diamminetetraaquacobalt (III) chloride
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1. A square planar complex is formed by hybridization of which atomic orbitals ? [AIEEE– 2002]
(1) s, px, py, dyz (2) s, px, py, dx2 – y2 (3) s, px, py, dz2 (4) s, px, py, dx y
3. In the complex [Fe(H2O)6]3+ [Fe(CN)6]3–, [Fe(C2O4)3]3– and [FeCl6]3– , more stability is shown by :
[AIEEE– 2002]
3+ 3– 3– 3–
(1) [Fe(H2O)6] (2) [Fe(CN)6] (3) [Fe(C2O4)3] (4) [FeCl6]
4. One mole of Co(NH3)5Cl3 gives 3 moles of ions on dissolution in water. One mole of this reacts with two moles of
AgNO3 to give two moles of AgCl. The complex is : [AIEEE– 2003]
(1) [Co(NH3)4Cl2]Cl.NH3 (2) [Co(NH3)4Cl]Cl2.NH3 (3) [Co(NH3)5Cl]Cl2 (4) [Co(NH3)3Cl3].2NH3
5. Ammonia forms the complex [Cu(NH3)4]2+ with copper ions in alkaline solution but not in acid solution. The
reason for it is : [AIEEE– 2003]
(1) in alkaline solution Cu(OH)2 is precipitated which is soluble in excess of alkali.
(2) copper hydroxide is amphoteric.
(3) in acidic solution hydration protects Cu2+ ions.
(4) in acidic solution protons coordinates with ammonia molecule forming NH4+ ions and NH3 molecules are not
available.
6. In the coordination compound K4[Ni(CN)4], the oxidation state of nickel is : [AIEEE– 2004]
(1) – 1 (2) 0 (3) + 1 (4) + 2
7. The co-ordination number of a central metal atom in a complex is determined by : [AIEEE– 2004]
(1) the number of only anionic ligands bonded to metal ion
(2) the number of ligands around a metal ion bonded by pi bonds
(3) the number of ligands around a metal ion bonded by sigma and pi bonds
(4) the number of ligands around a metal ion bonded by sigma bonds
9. Co-ordination compounds have great importance in biological systems. In this context, which statement is
incorrect ? [AIEEE– 2004]
(1) Carboxypeptidase–A is an enzyme and contains zinc.
(2) Haemoglobin is the red pigment of blood and contains iron.
(3) Cyanocobalmin is B12 and contains cobalt.
(4) Chlorophylls are green pigments in plants and contain calcium.
11. The correct order of magnetic moments (only spin value in BM) among is : [AIEEE– 2004]
(1) Fe(CN)64– > [CoCl4]2– > [MnCl4]2– (2) [MnCl4]2– > [Fe(CN)6]4– > [CoCl4]2–
4– 2– 2–
(3) [Fe(CN)6] > [MnCl4] > [CoCl4] (4) [MnCl4]2– > [CoCl4]2– > [Fe(CN)6]4–
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+
12. The oxidation state of Cr in [Cr(NH3)4Cl2] is : [AIEEE– 2005]
(1) 0 (2) +1 (3) +2 (4) +3
14. Which of the following will show optical isomerism ? [AIEEE– 2005]
2+ 2– 3– 3–
(1) [Cu(NH3)4] (2) [ZnCl4] (3) [Cr(C2O4)3] (4) [Co(CN)6]
15. The value of 'spin only' magnetic moment for one of the following configurations is 2.84 BM. The correct one is:
(1) d4 (in strong field ligand) (2) d4 (in weak field ligand) [AIEEE– 2005]
(3) d3 (in weak as well as strong field ligand) (4) d5 (in strong field ligand)
16. Which one of the following complexes would exhibit the lowest value of paramagnetic behaviour ?
[AIEEE– 2005]
3– 3– 3– 3–
(1) [Co(CN)6] (2) [Fe(CN)6] (3) [Mn(CN)6] (4) [Cr(CN)6]
17. Nickel (Z = 28) combines with a uninegative monodentate ligand X– to form a paramagnetic complex [NiX4]2– The
number of unpaired electron(s) in the nickel and geometry of this complex ion are, respectively :
(1) one, tetrahedral (2) two, tetrahedral [AIEEE– 2006]
(3) one, square planar (4) two, square planar
18. The IUPAC name for the complex [Co(NO2) (NH3)5]Cl2 is : [AIEEE– 2006]
(1) Nitrito-N-pentaamminecobalt(III) chloride (2) Nitrito-N-pentaamminecobalt(II) chloride
(3) Pentaamminenitrito-N-cobalt(II) chloride (4) Pentaamminenitrito-N-cobalt(III) chloride
20. How many EDTA (ethylenediaminetetraacetic acid) molecules are required to make an octahedral complex with
a Ca2+ ion ? [AIEEE– 2006]
(1) Six (2) Three (3) One (4) Two
21. The 'spin only' magnetic moment (in units of Bohr magneton, B) of Ni2+ in aqueous solution would be
(atomic number Ni = 28) [AIEEE– 2006]
(1) 2.84 (2) 4.80 (3) 0 (4) 1.73
22. Which one of the following has a square planar geometry? [AIEEE 2007, 2/120]
2– 2– 2– 2–
(1) [NiCl4] (2) [PtCl4] (3) [CoCl4] (4) [FeCl4]
(At. no. Co = 27, Ni = 28, Fe = 26, Pt = 78)
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COORDINATION COMPOUNDS
23. The coordination number and the oxidation state of the element 'E' in the complex [E(en)2(C2O4)] NO2 (when 'en'
is ethylene diamine) are, respectively, [AIEEE 2008, 3/105]
(1) 4 and 2 (2) 4 and 3 (3) 6 and 3 (4) 6 and 2
24. In which of the following octahedral complexes of Co (at no. 27), will the magnitude of 0 be the highest?
[AIEEE 2008, 3/105]
3– 3+ 3+
(1) [Co(C2O4)3] (2) [Co(H2O)6] (3) [Co(NH3)6] (4) [Co(CN)6]3–
25. Which of the following has an optical isomer ? [AIEEE 2009, 4/144]
2+ 3+ 3+
(1) [Co (en) (NH3)2] (2) [Co(H2O)4 (en)] (3) [Co (en)2 (NH3)2] (4) [Co (NH3) 3 Cl]+
26. Which of the following pairs represents linkage isomers ? [AIEEE 2009, 4/144]
(1) [Pd(PPh3)2 (NCS)2] and [Pd(PPh3)2 (SCN)2] (2) [Co(NH3)5 NO3] SO4 and [Co (NH3)5 (SO4)] NO3
(3) [PtCl2 (NH3)4 Br2 and [Pt Br2 (NH3)4] Cl2 (4) [Cu (NH3)4] [Pt Cl4] and [Pt (NH3)4 [CuCl4]
27. A solution containing 2.675 g of CoCl3 . 6 NH3 (molar mass = 267.5 g mol–1) is passed through a cation
exchanger. The chloride ions obtained in solution were treated with excess of AgNO3 to give 4.78 g of AgCl
(molar mass = 143.5 g mol–1). The formula of the complex is (At. mass of Ag = 108 u) [AIEEE 2010, 8/144]
(1) [Co(NH3)6 ] Cl3 (2) [CoCl2 (NH3)4] Cl (3) [CoCl3(NH3)3] (4) [CoCl(NH3)5] Cl2
28. Which one of the following has an optical isomer ? [AIEEE 2010, 4/144]
2+ 3+ 3+
(1) [Zn(en)(NH3)2] (2) [Co(en)3] (3) [Co(H2O)4(en)] (4) [Zn(en)2]2+
(en = ethylenediamine)
29. Which of the following facts about the complex [Cr(NH3)6] Cl3 is wrong ? [AIEEE 2011, 4/144]
(1) The complex involves d2 sp3 hybridisation and is octahedral is shape
(2) The complex is paramagnetic
(3) The complex is an outer orbital complex
(4) The complex gives white precipitate with silver nitrate solution
30. The magnetic moment (spin only) of [NiCl4]2– is : [AIEEE 2011, 4/144]
(1) 1.82 BM (2) 5.46 BM (3) 2.82 BM (4) 1.41 BM
31. Which among the following will be named as dibromidobis(ethylene diamine) chromium(III) bromide ?
[AIEEE 2012, 4/120]
(1) [Cr(en)3 Br3 (2) [Cr(en)2 Br2] Br (3) [Cr (en)Br4] –
(4) [Cr (en) Br2] Br
32. Which of the following complex species is not expected to exhibit optical isomerism ? [AIEEE 2013]
(1) [Co(en)3]3+ (2) [Co(en)2Cl2]+ (3) [Co(NH3)3Cl3] (4) [Co(en)(NH3)2Cl2]+
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COORDINATION COMPOUNDS
NCERT QUESTIONS
2. FeSO4 solution mixed with (NH4)2SO4 solution in 1 : 1 molar ratio gives the test of Fe2+ ion but CuSO4 solution
mixed with aqueous ammonia in 1 : 4 molar ratio does not give the test of Cu2+ ion. Explain why?
3. Explain with two examples each of the following: coordination entity, ligand, coordination number, coordination
polyhedron, homoleptic and heteroleptic.
4. What is meant by unidentate, didentate and ambidentate ligands? Give two examples for each.
5. Specify the oxidation numbers of the metals in the following coordination entities :
(i) [Co(H2O)(CN)(en)2]2+ (ii) [CoBr2(en)2]+ (iii) [PtCl4]2–
(iv) K3[Fe(CN)6]ƒÊ (v) [Cr(NH3)3Cl3]
8. List various types of isomerism possible for coordination compounds, giving an example of each.
9. How many geometrical isomers are possible in the following coordination entities?
(i) [Cr(C2O4)3]3– (ii) [Co(NH3)3Cl3]
12. Write all the geometrical isomers of [Pt(NH3)(Br)(Cl)(py)] and how many of these will exhibit optical isomers?
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COORDINATION COMPOUNDS
14. What is the coordination entity formed when excess of aqueous KCN is added to an aqueous solution of copper
sulphate? Why is it that no precipitate of copper sulphide is obtained when H2S(g) is passed through this
solution?
15. Discuss the nature of bonding in the following coordination entities on the basis of valence bond theory :
(i) [Fe(CN)6]4– (ii) [FeF6]3– (iii) [Co(C2O4)3]3– (iv) [CoF6]3–
16. Draw figure to show the splitting of d orbitals in an octahedral crystal field.
17. What is spectrochemical series? Explain the difference between a weak field ligand and a strong field ligand.
18. What is crystal field splitting energy? How does the magnitude of 0 decide the actual configuration of d orbitals
in a coordination entity?
21. [Fe(CN)6]4– and [Fe(H2O)6]2+ are of different colours in dilute solutions. Why?
23. Give the oxidation state, d orbital occupation and coordination number of the central metal ion in the following
complexes:
(i) K3[Co(C2O4)3] (iii) (NH4)2[CoF4] (ii) cis-[Cr(en)2Cl2]Cl (iv) [Mn(H2O)6]SO4
24. Write down the IUPAC name for each of the following complexes and indicate the oxidation state, electronic
configuration and coordination number. Also give stereochemistry and magnetic moment of the complex :
(i) K[Cr(H2O)2(C2O4)2].3H2O (ii) [Co(NH3)5Cl-]Cl2
(iii) CrCl3(py)3 (iv) Cs[FeCl4] (v) K4[Mn(CN)6]
25. What is meant by stability of a coordination compound in solution? State the factors which govern stability of
complexes.
27. Discuss briefly giving an example in each case the role of coordination compounds in :
(i) biological systems (ii) medicinal chemistry and
(iii) analytical chemistry (iv) extraction/metallurgy of metals.
28. How many ions are produced from the complex Co(NH3)6Cl2 in solution?
(i) 6 (ii) 4 (iii) 3 (iv) 2
29. Amongst the following ions which one has the highest magnetic moment value?
(i) [Cr(H2O)6]3+ (ii) [Fe(H2O)6]2+ (iii) [Zn(H2O)6]2+
32. What will be the correct order for the wavelengths of absorption in the visible region for the following :
[Ni(NO2)6]4–, [Ni(NH3)6]2+, [Ni(H2O)6]2+ ?
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EXERCISE # 1
PART # I
A-1. (A) A-2. (B) A-3. (D) A-4. (D) A-5. (A) A-6. (D) A-7. (B)
A-8. (A) A-9. (C) B-1. (C) B-2. (C) B-3. (A) B-4. (B) B-5. (D)
B-6. (C) B-7. (B) B-8. (B) B-9. (C) B-10. (B) B-11. (A) B-12. (C)
B-13. (D) B-14. (C) C-1. (A) C-2. (C) C-3. (A) C-4. (A) C-5. (C)
C-6. (B) C-7. (C) C-8. (A) C-9. (B) C-10. (B) C-11. (B) C-12. (C)
C-13. (D) C-14. (C) D-1. (D) D-2. (A) D-3. (A) E-1. (D) E-2. (C)
E-3. (A) E-4. (A) E-5. (A) E-6. (C) E-7. (D) E-8. (C) E-9. (C)
E-10. (C) E-11. (C) F-1. (C) F-2. (B) F-3. (D) G-1. (A) G-2. (C)
G-3. (A) G-4. (C) G-5. (A) G-6. (C) G-7. (D) G-8. (C) G-9. (B)
G-10. (D) G-11. (D) G-12. (C) G-13. (C) G-14. (C) H-1. (C) H-2. (B)
H-3. (B) H-4. (C) H-5. (C) I-1. (D) I-2. (D) I-3. (C) I-4. (A)
I-5. (D) I-6. (C) I-7. (D)
PART # II
1. (B) 2. (D) 3. (A) 4. (B) 5. (D) 6. (C) 7. (B)
8. (D) 9. (A – p, q, r) ; (B – p, s); (C – q, r) ; (D – q, r)
10. (A – p, r, s, t) ; (B – q) ; (C – q) ; (D – p, r, s) 11. (A– p,s) ; (B – p, s, t) ; (C – s, t) ; (D – p, s)
12. (A) 13. (C) 14. (A) 15. (B) 16. (A) 17. (B) 18. (C)
19. (A) 20. (D) 21. (B) 22. (C) 23. False 24. True 25. False
26. False 27. True 28. False 29. True 30. True 31. True 32. False
EXERCISE # 2
PART # I
1. (A) 2. (A) 3. (A) 4. (C) 5. (A) 6. (D) 7. (B)
8. (C) 9. (B) 10. (D) 11. (B) 12. (D) 13. (B) 14. (A)
15. (D) 16. (A) 17. (A) 18. (C) 19. (C) 20. (A) 21. (C)
22. (D) 23. (C) 24. (C) 25. (B) 26. (C) 27. (D) 28. (D)
29. (C) 30. (ACD) 31. (BCD) 32. (BD) 33. (ABD) 34. (BD) 35. (CD)
26. (ABC) 37. (AD) 38. (BCD) 39. (ABCD)
PART # II
1. (c) [Fe(CO)5], Pentacarbonyliron(0)
(d) [Fe(C2O4)3]3–, Trioxalatoferrate(III) OR Tris(oxalato)ferrate(III)
(e) [Cu(NH3)4]SO4, Tetraamminecopper(II) sulphate
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5. (i) H12O6Cl3Cr
A should be [Cr(H2O)6]Cl3 because it is not reacting with H2SO4 if there would have some moles of water outer the
coordination sphere then it will be reacting with H2SO4
(B) weight of H12O6Cl3Cr = 266.5
6.73
266.5 × = 17.96 18 (H2O weight)
100
It means one mole of H2O in B complex outer the coordination sphere
B = [Cr[H2O]5Cl]Cl2.H2O
13 .5
(C) 266.5 × 36 (2H2O weight)
100
It means C = [Cr(H2O)4Cl2]Cl.2H2O
(ii) A = [Cr (H2O)6]Cl3 ; B = [Cr(H2O)5Cl]Cl2.H2O ; C = [Cr(H2O]4Cl2]Cl.2H2O
(iii) EAN = 33
(iv) C – 1 mole AgCl ppt; B – 2 mole AgCl ppt; A – 3 mole AgCl ppt
6. (i) [Cr(NH3)4Cl Br]Cl [Cr(NH3)4Cl Br]+ + Cl– ; Ag+ + Cl– AgCl (white) ; soluble in dilute NH3.
[Cr(NH3)4Cl2]Br [Cr(NH3)4Cl2]+ + Br– ; Ag+ + Br– AgBr (yellow) ; soluble in conc. NH3.
So, A = [Cr(NH3)4Cl Br]Cl and B = [Cr(NH3)4Cl2]Br.
(ii) In both complexes chromium is in +3 oxidation state. Chromium with 3d3 configuration has 3 unpaired
electrons with weak field as well as strong field ligand. So, the hybridisation scheme is as follow :
(iii) = n (n 2) = 15 (iv) EAN = 24 – 3 + 12 = 33 (v) Yes, both have two ions per formula unit.
(vi) AgCl + 2NH3 [Ag(NH3)2]Cl ; AgBr + 2NH3 [Ag(NH3)2]Br
– – 2+ 2+
edta
7. (a) Cr
Ru
en
[Ru(en)3]2+ enantiomers
[Cr(edta)] enantiomers
–
Cl
+
Pt
dien
+
[Pt(dien)]
Neither [Cr(edta)]– nor [Ru(en)3]2+ has a mirror plane or a centre of inversion; so both are chiral (they also have
no higher Sn axis); [Pt (dien)Cl]+ has a plane of symmetry and hence is achiral.
(b) Carbonylhydridobis(trimethylphosphine)irridium(I).
r is in +1 oxidation state; 5d8 configuration has higher CFSE and thus the complex is square planar.
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5d 6s 6p
[rH(CO)(PMe3)2]
2
dsp hybridisation
Geometry = Square planar
Magnetic moment = O (all electrons are paired).
8. cis, trans and optical isomers are possible.
(a)
Both cis and trans isomers do not show optical activity because of the presence of plane and centre of symmetries.
(b) It will not exhibit geometrical isomerism as it exists only in one form as given below.
(c) In tetrahedral geometry all positions are adjacent to each other so it will not exhibit geometrical isomerism.
(d) In square planar geometry there is plane of symmetry. So it does not show optical isomerism.
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(e) It will not exhibit geometrical isomerism as it exists only in one form as given below.
SCN
SCN
3+
en Co
SCN
SCN
(f) Cr(NH3)2(H2O)2Cl2]+ is of Ma2b2c2 type which has following isomeric forms.
(aa)(bb)(cc)
(aa)(bc)(bc)
(bb)(ac)(ac)
(cc)(ab)(ab)
(ab)(ac)(bc)
(g)
11. (a) No ; (b) Yes ; (c) Yes ; (d) Yes ; (e) Yes ; (f) No.
t2g
t Number of unpaired electrons = 4
eg
dx2– y2
dyz dzx
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EXERCISE # 3
PART # I
1. In [Co(NH3)6]3+, the oxidation state of cobalt is +3 and coordination number is 6. So
Co3+ ion
NH3 is stronger field ligand. So it compels for the pairing of electrons. Then
[Co(NH3)6]3+
d2sp3 - hybridisation
Thus with 6 coordination number, the complex [Co(NH3)6] is octahedral as given below.
Ni2+
CN– is stronger field ligand. So it compels for the pairing of electrons. Then
[Ni(CN)4]2–
dsp2 - hybridisation
Thus with 4 coordination number four, the complex is square planar as given below
In [Ni(CO)4], the oxidation state of nickel is zero and the coordination number is four. So
Ni (O)
CO is strong field ligand. So it compels for the pairing of electrons; so nickel under goes rearrangement. Then
[Ni(CO)4]
sp3 - hybridisation
Thus with 4 coordination number, the complex is tetrahedral as given below.
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2. (A)
3. As form(A) gives white precipitate with AgNO3 solution and precipitate is readily soluble in dilute aqueous
ammonia, the complex must be having the Cl– ion in the ionisation sphere. Hence(A) must be having the formula
[Cr(NH3)4ClBr]+Cl–.
Ag+ + Cl– AgCl (white).
AgCl + 2NH3 [Ag(NH3)2]+Cl– (soluble complex).
Similarly form(B) gives pale yellow precipitate with AgNO3 and precipitate is soluble in concentrated ammonia,
the complex must be having the Br– in the ionisation sphere. Hence(B) must be having the formula [Cr(NH3)4Cl2]+Br–.
Ag+ + Br– AgBr (pale yellow).
AgBr + 2NH3 [Ag(NH3)2]+ Br (soluble complex).
In both complexes, the chromium is the central metal ion with +3 oxidation state. In both, the ammonia is a
strong field ligand so it compels for pairing of electrons. Thus,
[Cr(NH3)4ClBr]+ or [Cr(NH3)4Cl2]+
4. In[NiCl4]2– nickel is in+2 oxidation state and Cl– is weak field ligand. So,
[Ni(Cl)4]2–
Tetrahedral
In[Ni(CN)4]2– nickel is in+2 oxidation state and CN– is strong field ligand, So it compels for pairing of electrons.
Then,
[Ni(CN)4]2–
Square planar
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As the CN– and NH3 are strong fields ligands, they compel for pairing of electrons. So,
[Cr(NO)(CN)4(NH3)]2– =
Hence, the oxidation state of chromium is +1 (having 3d5 configuration). So according to charge on the complex
NO should be NO+ and the structure of this complex is octahedral with d2sp3 hybridisation as given below
6. (D) 7. (C)
NH 4 OH
8. Ni2+ + 2dmg [Ni(dmg)2] (bright red).
It acquires stability through chelation and intra molecular H-bonding.
In [Ni(dmg)2] the nickel is in +2 oxidaiton state and to have square planar geometry because of chelation the
pairing of electrons takes place. So
[Ni(DMG)2]
As all electrons are paired, so complex is diamagnetic. Nickel with coordination number four will have the
structure as given below.
O -------- H – O
CH3 – C = N N = C – CH3
+2
Ni
H 3C – C = N N = C – CH3
O – H -------- O
9. (A)
SCN F ( excess)
10. (a) Fe3+
blood red[Fe((H O) (SCN)]2+ (A)
2 5
colourless(B) [Fe(F6)]3– + SCN– + 5H2O.
(Excess )
(A) Pentaaquathiocyanato-S-iron(III) ; (B) Hexafluoridoferrate(III)
(b) Fe3+ CFSE electron configuration, t2g1, 1, 1 1,1
eg ; as F– being weak field ligand does not compel for pairing of
electrons. So it contains five unpaired electrons.
So, = 5 (5 2) = 5.93 B.M.
The magnetic moment value of B is 5.93 B.M.
11. (A) 12. (A) 13. (C) 14. (C) 15. (B)
16. (A) – p, q, s ; (B) – p, r, s ; (C) – q, s ; (D) – q, s 17. (C) 18. (B) 19. (B) 20. (A)
21. (C), (D) 22. (A) 23. (C) 24. (B) 25. (B) 26. 3 27. (B)
28. (C) 29. (A) 30. (D) 31. (C)
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PART # II
1. (2) 2. (2), (3) 3. (3) 4. (3) 5. (4) 6. (2) 7. (4)
8. (1) 9. (4) 10. (1) 11. (4) 12. (4) 13. (2) 14. (3)
15. (1) 16. (1) 17. (2) 18. (4) 19. (2) 20. (3) 21. (1)
22. (2) 23. (3) 24. (4) 25. (3) 26. (1) 27. (1) 28. (2)
29. (3) 30. (3) 31. (2) 32. (3)
EXERCISE # 4
1. (i) [Co(NH3)4(H2O)2]Cl3 (ii) K2[Ni(CN)4] (iii) [Cr(en)3]Cl3
(iv) [Pt(NH3)BrCl(NO2)]– (v) [PtCl2(en)2](NO3)2 (vi) Fe4[Fe(CN)6]3
3. (i) Both geometrical (cis-, trans-) and optical isomers for cis can exist.
(ii) Two optical isomers can exist.
(iii) There are 10 possible isomers. (Hint: There are geometrical, ionisation and linkage isomers possible).
(iv) Geometrical (cis-, trans-) isomers can exist.
4. The ionisation isomers dissolve in water to yield different ions and thus react differently to various reagents :
[Co(NH3)5Br]SO4 + Ba2+ BaSO4 (s)
[Co(NH3)5SO4]Br + Ba2+ No reaction
[Co(NH3)5Br]SO4 + Ag+ No reaction
[Co(NH3)5SO4]Br + Ag+ AgBr (s)
6. In Ni(CO)4, Ni is in zero oxidation state whereas in NiCl42–, it is in +2 oxidation state. In the presence of CO
ligand, the unpaired d electrons of Ni pair up but Cl– being a weak ligand is unable to pair up the unpaired
electrons.
7. In presence of CN–, (a strong ligand) the 3d electrons pair up leaving only one unpaired electron. The hybridisation
is d2sp3 forming inner orbital complex. In the presence of H2O, (a weak ligand), 3d electrons do not pair up. The
hybridisation is sp3d2 forming an outer orbital complex containing five unpaired electrons, it is strongly paramag-
netic.
8. In the presence of NH3, the 3d electrons pair up leaving two d orbitals empty to be involved in d2sp3 hybridisation
forming inner orbital complex in case of [Co(NH3)6]3+. In Ni(NH3)62+, Ni is in +2 oxidation state and has d8
configuration, the hybridisation involved is sp3d2 forming outer orbital complex.
9. For square planar shape, the hybridisation is dsp2. Hence the unpaired electrons in 5d orbital pair up to make
one d orbital empty for dsp2 hybridisation. Thus there is no unpaired electron.
11. The overall dissociation constant is the reciprocal of overall stability constant i.e. 1/ 4 = 4.7 × 10–14
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