ALTITUDE CLASSES

23 COORDINATION
COMPOUNDS

Co-ordination compounds in which the central metal atom is linked Representation of Complexes
to a number of ions or neutral molecules by coordinate bonds, i.e. Werner’s representation for Fe(NH3)6Cl3
by donation of ions pairs of e–1 s by these ions or neutral molecules
to the central metal atom. Cl
NH3
DOUBLE SALT AND COMPLEX COMPOUND H 3N
NH3
The main difference between a double salt (like alums, Mohr’s Fe Cl
salt, etc.) and a complex (like ferrocyanide) ion is that former H3N NH3
dissociates completely into ions in aqueous solution and does NH3 Cl
not contain any coordinate bond while later does not dissociates Dotted lines indicate primary valency and solid lines indicate
completely into ions and always contains coordinate bonds. secondary valency of metal ion.
WERNER’S THEORY OF COMPLEXES S OME IMPORTANT TERMS US ED IN CO -
The main postulates are: ORDINATION COMPOUNDS
(i) Every metal forming a complex exhibits two types of valencies
Primary valency and Secondary valency. Co-ordination Entity/ Co-ordination Sphere
(ii) Primary valency is ionisable in nature whereas secondary The central metal atom/ ion and the ligands which are directly
valency is non-ionisable. attached to it are enclosed in square brackets and are collectively
(iii) Primary valency is also called oxidation state. Secondary called coordination entity. The ionizable groups are written outside
valency is also called co-ordination number of metal the brackets and are called counter ions.
ex: Pt NH 3 Cl 4 , primary valency is 4 (from 4Cl– ) Central Atom / ion:
6
In a co-ordination entity, the atom / ion to which a fixed number of
whereas secondary valency is 6 (from 6NH3)
ions / groups are bound in a definite geometrical arrangement
(iv) Primary valencies are satisfied by negative ions whereas
secondary valencies are satisfied by negative ion or neutral around it, is called central atom / ion.
molecules. They are also referred to as Lewis acids
(v) Secondary valencies are directional and determine geometry Ligands
of the complex. On the other hand, primary valencies are non These are ions / molecules which bound to central atom / ion in
directional. co-ordination entity. Ligands may be ions (ex: Cl–), small molecules
Experimental evidence to Werner’s theory of complexes can be like H2O or NH3, larger molecules like H2N CH2CH2NH2 or
provided based on : N(CH2CH2NH2)3 or even macromolecules.
(i) Precipitation of primary valencies on the addition of a suitable The number of co-ordinating or ligating groups present in a ligand
reagent. is called its denticity. Based on this, ligands are classified as:
(ii) Electrical conductance of complexes

Ligands

Unidentate /
Didentate/Bidentate Polydentate
monodentate
If two donor atoms are If several donor atoms are
If one donor atom is present in its molecule present in its molecule
present in its molecule which can coordinate which can coordinate
which can coordinate 2–
– Ex ; NH2CH2CH2NH2,C2O4 Ex: EDTA (hexadentate)
Ex: Cl , H2O, NH3
 ALTITUDE CLASSES
CHEMISTRY
Chelating Ligands NOMENCLATURE OF CO -ORDINATION
If the ligands with two or more electron donor groups (or co- COMPOUNDS
ordinating groups) positioned in such a way that they form five or
Formulas of Mononuclear Co-ordination
six membered ring with central metal ion, then the ligands are
Compounds
known as chelating ligands and the ring formed is called chelate
ring. The complex which is thus formed is termed as metal chelate Following rules are applied:
or simply chelate while this property is called chelation. (i) The central atom is listed first.
(ii) The ligands are then listed in alphabetical order. The
Chelating ligands form more stable complexes. Complexes formed
placement of a ligand in the list does not depend on its charge.
by ligands with smaller groups are more stable as compared to
(iii) Polydentate ligands are also listed alphabetically.
complexes formed by ligand with larger group. (iv) In case of abbreviated ligands (e.g., en for ethane-1, 2-
Chelates are used in softening of hard water, in separation of diamine),the first letter of the abbreviation is used to determine
lanthanoids and actinoids, in qualitative analysis of metals etc. the position of the ligand in the alphabetical order.
Ambidentate Ligands (v) The formula of the entire coordination entity, whether charged
Ligands which can bind through two different sites are called or not, is enclosed in square brackets.
ambidentate ligands. For ex: NO 2 , SCN , etc. (vi) There should be no space between the ligands and the metal
within a co-ordinatiion sphere.
Co-ordination Number (vii) If the formula is written without the counter ion, the charge is
The number of coordinate bonds formed with the central metal indicated outside the square bracket as a superscript.
atom/ion by the ligands. For determining co-ordination number (viii) The charge of the cation (s) is balanced by the charge of the
only sigma bonds are considered not pi-bonds even if formed. anion (s).
Naming of Mononuclear Coordination Compounds
For ex: Pt Cl6 2 , Co-ordination number of Pt = 6 Following rules are used:
(i) The cation is named first in both positively and negatively
3
Fe C 2 O 4 3 , Co-ordination number of Fe = 6 charged co-ordination entities.
(ii) The ligands are named in alphabetical order before the name
Co-ordination Polyhedron of the central atom / ion.
It is the spatial arrangement of ligand atoms which are directly (iii) The ligands can be neutral, anionic or cationic.
attached to the central atom / ion. (a) Neutral ligands are named as the molecule e.g. C5H5N
The polyhedron can be octahedral, square planar, square is named as pyridine,
pyramidal, trigonal bipyramidal or tetrahedral. (C6H5)3P as Triphenyl phosphine,
Oxidation Number of Central Atom H2N–CH2–CH2–NH2 as ethylene diamine.
The neutral ligands which are not named as the molecule
It is the charge which the central atom would carry if all the ligands
are
are removed along with the e– pairs that are shared with the central
CO carbonyl
3 NO nitrosyl
atom. For example : Oxidation number of Cu in Cu CN 4 is
H2O aqua
+1 and is written as Cu (I). NH3 amine
Homoleptic and Heteroleptic Complexes (b) Negative ligands end in ‘O’, i.e.,
Complexes in which a metal is bound to only one kind of donor Cl– chloro, SO42– sulphato NO2– Nitro
–
ONO nitrito, OH– hydroxo, NH2– amido
3
groups are called homoleptic. For ex: Cu NH 3 2–
NH imido NO3– nitrato, CO32– carbonato
6
Complexes in which a metal is bound to more than one kind of CH3COO– acetato, CN– cyano
donor groups are heteroleptic : For ex: [Co(NH3)4Cl2]
(c) Positive ligands end in ‘ium’ ex : NH2 NH3
Homonuclear and Polynuclear Complexes :
Complexes in which only one metal atom is present are Hydrazinium, NO2 (nitronium), NO (nitrosonium)
homonuclear. (iv) Prefixes mono, di, tri, etc are used to indicate the number of
Example : K3[Fe (C2O4)3] individual ligands in co-ordination entity.
Complexes in which more than one metal atoms are present are (v) Oxidation state of the metal in cation, anion or neutral co-
known as polynuclear. ordination entity is indicated by Roman numeral in parenthesis.
(vi) If the complex ion is a cation, the metal is named same as the
NH2 element.
For example : [Co (NH3)6] Cl3
(en)2 Co (Cationic complex is present so metal is without any suffix)
Example : Co(en)2 (SO4)2
Hexaaminecobalt (III) chloride.
If the complex ion is an anion, the name of the metal ends with
OH the suffix - ate.
 ALTITUDE CLASSES
COORDINATION COMPOUNDS
For example : K4[Fe(CN)6] (ii) Mabcd Three isomers are possible
(anionic complex is present so suffix ate is added with metal’s a b a d a b
name) Potassium hexacyanoferrate (II)
(vii) The neutral complex molecule is named similar to that of the
M M M
complex cation.
(viii) When bidentate ligands are coordinated to the metal ion,
their repetition is indicated by prefixes like bis, tris, tetrakis d c c b c d
(i) (ii) (iii)
etc. For example :
(a) [Fe (en)3] Cl3 Example : [Pt(NH3)(NH2OH)(NO2)(py)NO2.
Trisethylenediamineiron (III) chloride Octahedral complexes showing this behaviour are of type:
(b) [Ni (gly)2] (i) Ma 4 b2
Bisglycinatonickel (II) b b
ISOMERISM IN CO-ORDINATION COMPOUNDS a b a a
Isomers are two or more compounds that have the same chemical ex: Co NH3 Cl2 M M
4
formula but a different arrangement of atoms.Co-ordination
compounds show two main types of isomerism: a a a a
a b
Structural Isomerism
Cis Trans
(i) Linkage isomerism: It arises in complexes containing [ Ma4 b2 ]
ambidentate ligand. For ex: SCN. It can bind through N or S
to give M - NCS or M - SCN. For example [Cr(H2O)5(SCN)]2+ (ii) M a2 (b – b)2 i.e. with bidentate ligands b – b (cis and trans
and [Cr(H2O)5(NCS)]2+ are linkage isomers. forms)
(ii) Coordination isomers : This type of isomerism occurs when ex: CoCl2(en)2.
both cation and anion of a salt are complex. The isomerism (iii) Ma3b3 (facial and meridional isomers).
arises by the interchange of ligands between the two complex
b b
ions. a a
b b
For example : [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
(iii) Ionisation Isomerism: It arises when the counter ion in a M M
complex salt is itself a potential ligand and can displace ligand
which can then become the counter ion. This type of isomers a b a a
a b
yields different types of ions in solution.
Cis Trans
For ex: Co NH 3 5 SO 4 Br and Co NH 3 5 Br SO 4 [ Ma3b3 ]

(iv) Solvate/ Hydrate Isomerism: Octahedral complexes of general formula, Mabcdef, can have
The complexes which differ with respect to the number of fifteen geometrical isomers.
water molecules attached to the metal ion as ligands are called (II) Optical Isomerism
hydrate isomers. It is shown by compounds which cannot be superimposed.An
For e.g. - Cr(H2O)6Cl3 has three possible structures optically active complex is one which is asymmetric in nature
i.e., not divisible into two identical halves.
(a) [Cr(H2O)6]Cl3 violet It has two forms, dextro (d) and laevo (l), arise depending
(b) [Cr(H2O)5Cl] Cl2.H2O green upon the direction in which they rotate the plane of polarised
(c) [Cr(H2O)4Cl2]Cl . 2H2O dark green. light.
This isomerism is common in octahedral complex involving
Stereo Isomerism
bidentate ligands.
(I) Geometrical Isomerism
3 2+
Geometrical isomerism is most important in compounds with ex: Co en 3
, cis is isomer of PtCl 2 en 2
coordination numbers 4 and 6. 4-coordinated complexes with
For complexes with coordination number 4, square planar
tetrahedral geometry do not exhibit cis-trans isomerism.
complexes do not show optical isomerism but tetrahedral
Square planar complexes showing this behaviour are of type: complexes having bidentate ligands, ex : [Ni(gly)2] shows
(i) Ma 2 b2 optical isomerism.
a b a a Other examples are [Co(en)3]3+, [CoCl2(en)2]+ etc.
BONDING IN CO-ORDINATION COMPOUNDS
M M
Valence Bond Theory (VBT)
b a b b
Trans–isomer Cis–isomer
(i) According to this theory, metal - ligand bonds are formed by
the overlap of metal orbitals with those of ligands i.e., by
[Ma2b2 ] donation of e– -pairs by the ligands to empty hybridized
ex: Pt (NH3)2 Cl2 orbitals of metal.
 ALTITUDE CLASSES
CHEMISTRY
For e.g. -In the formation of [Fe(NH3)6]3+ , Fe+3 ion provides Inner and Outer Orbital Complexes
six vacant orbitals. The empty ‘d’ orbitals involved in hybridisation may be inner
In [Cu(NH3)4]2+, Cu2+ ion provides four vacant orbitals. (n – 1)d or outer nd orbitals. The complexes thus formed are
called as Inner orbital complexes and Outer orbital complexes
(ii) The metal orbitals undergo hybridisation, to give a set of
respectively.
hybrid orbitals of equal energy. In case of inner orbital complex the electrons of the metal are made
(iii) The number of vacant orbitals provided is equal to the to pair up, so the complex will be either diamagnetic or less
coordination number of metal ion. paramagnetic. This type of complex is also known as low spin
(iv) Octahedral, square planar and tetrahedral complexes are formed complex. For outer orbital complex number of unpaired electrons
as a result of d2sp3 (or sp3d2), dsp2 and sp3 hydridisation will be large as the configuration of the metal remains unchanged.
respectively of the central metal atom or the ion. This type of complex is also known as high spin complex.
A few examples are:

Complex Hybridisation Magnetic behaviour Nature

(CN = 6)
[Cr(NH3)6]
3+ 2
d sp
3 paramagnetic inner orbital
3– 2 3
[Fe(CN)0] d sp octahedral slightly paramagnetic inner orbital
4– 2 3
{Fe(CN)6] d sp inner orbital
diamagnetic
3–
paramagnetic outer orbital
[CoF6] 3 2
sp d
(CN = 4)
0 3 diamagnetic —
[Ni (CO4)] sp tetrahedral
2+ 3
[Zn(NH3)4] sp diamagnetic —
2–
[Ni(CN)4] dsp
2
Square diamagnetic —
2+ 2 planar
[Cu(NH3)4] dsp paramagnetic —
(CN = 5)
3 trigonal diamagnetic
Fe (CO)5 dsp bipyramidal
The d-orbitals present in metal have the same energy in the free
Note : Number of unpaired electrons present ( n(n 2) BM)
state. This is called degenerate state of d-orbital. But, when a
can be calculated by determining magenatic moment value complex is formed the ligands destroy the degeneracy of these
experimentally. Thus type of hybridisation involved in complex orbitals. This effect is known as Crystal field splitting of d- orbitals.
can be predicted.
Crystal Field Theory for Octahedral Complexes :
Crystal Field Theory When a ligand approaches the metal ion, the ‘d’ orbitals of the
This theory considers M - L bond to be ionic arising from metal ion undergo splitting forming two sets i.e., higher energy
electrostatic interaction. set, eg of dx 2– y 2 and dz 2 and a lower energy set, t2g of dxy’ dyz,
and dxz
This is shown diagrammatically as:
Crystal field
splitting energy ( 0 )
dx2–y 2 dz 2

0.6
Energy

0 eg

0
Average energy of
orbitals in a spherical 0.4 0 dxy dyz dxz
crystal field

t2g
d-orbitals in free ion
Figure : Splitting of d-orbitals in octahedral field
 ALTITUDE CLASSES
COORDINATION COMPOUNDS
The difference of energy between the two sets of d-orbitals is STABILITY OF CO-ORDINATION COMPOUNDS
called crystal field splitting energy or crystal field stabilization
energy (CFSE). It is usually represented by the symbol o. The stability of a complex in solution can be expressed in terms of
For any given metal cation, the magnitude of o depends upon equilibrium constant of the dissociation equilibrium
the nature of the ligands For a general complex dissociating reaction
Spectro chemical series MLbn Ma nLx
In general, ligands can be arranged in a series in order of increasing
field strength as given below: [M a ][Lx ]n
I– < Br– < SCN– < Cl– < S2– < F– < OH– Ki
[MLbn ]
< C 2 O24 < O2– < H2O < NCS– < EDTA4– < NH3 < en < NO2–
Ki = instability constant
< CN– < CO
This series is called spectrochemical series. Ma nLx MLbn
Pairing of the two sets of d-orbital depends on the magnitude of
[MLbn ]
o and P ( o , CFSE and P pairing energy)
n
4 e0 6 [M a ][Lx ]n
If o > P, EC is t 2g g . Upto d pairing will occur in the t2g and
eg. will remain vacant. Ligands which produce this effect are called n stability constant ( = 1/Ki)
strong field ligands and form low spin complex. Thus more will be stability constant more will be stability of
complex.
If o < P, EC is t 2g 3 e1g . For d5 configuration t 32 g eg2 ligands
For the reaction, M + 4L ML4, overall stability constant is
which produce this effect are called weak field ligands and form
high spin complexes. given by 4
4 ML 4 / M L whereas the stepwise stability
4 constants are:
For tetrahedral complex, t 0
9 (i) M+L ML
Splitting pattern for tetrahedral complexes is just the reverse of
the splitting patterns of the octahedral complexes t is so small K1 ML / M L
that it is unable to force the electrons to pair up.
Here, energy of eg < energy of t2g. (ii) ML + L ML 2
Colour of the complexes
The coloured nature of solutions of coordination compounds can K2 ML2 / ML L
also be explained on the basis of crystal field theory, because in
coordination compounds the energy difference between two sets (iii) ML 2 + L ML3
of d-orbitals is usually small (as explained by crystal field splitting)
thus, excitation of an electron from lower energy to higher energy K3 ML3 / ML 2 L
is very easy and can be achieved even by the absorption of low
(iv) ML3 + L ML 4
energy radiations of visible region. As the result of the absorption
of such selected wavelengths of visible light, the complexes K4 ML4 / ML3 L
appeared coloured.
Different complexes exhibit different colours when either metal is and, K1 K 2 K3 K4
4
different or ligands are different.
In absence of ligand, crystal field splitting does not occur and or, K1 K 2 K3 Kn
n
hence, the substance is colourless. For ex: CuSO4. 5H2 O is blue
but anhydrous CuSO4 is white. Note (i) Greater is the charge on central metal ion, greater will be
The size of depends on - the stability of the complex
(i) Nature of the ligand : In Spectrochemical series decreases (ii) Greater will be the basic strength of ligand stable will be
as shown below the complex
(iii) Formation of chelate rings increases the stability of the
I – Br – Cl – OH – F C2O 42 H 2O CNS– < complex.
weak ligands IMPORTANCE OF CO-ORDINATION COMPOUNDS
– –
NH 3 en NO2 CN CO (i) In qualitative analysis : In salt analysis, the presence of a
strong ligands number of basic radicals is confirmed by converting them
(ii) Oxidation state of the metal : is greater for M3+ than for into suitable complexes which have definite colours.
M2+ For ex : Fe3+ forms a prussian blue complex with potassium
(iii) Position of the metal in the periodic table: For a given ligand ferrocyanide solution :
and oxidation state of the metal, increases going down in
a group eg. 4FeCl3 3K 4 [Fe(CN)6 ] Fe 4 [Fe(CN) 6 ]3 12KCl
is greater in [Ru (NH3)6]3+ than in [Fe(NH3)6]3+ Ferri-ferrocyanide
(Prussian blue)
 ALTITUDE CLASSES
CHEMISTRY
(ii) In extraction of metals : The noble metals like silver and gold Bonding in Metal Carbonyls
are extracted from their ores through the formation of cyanide Bond is formed between transition metal and C of CO group.
complexes, [Ag(CN)2]– and [Au(CN)2]–. These carbonyls can have tetrahedral, trigonal bipyramidal or
(iii) In biological systems : A number of biologically important octahedral structure.
compounds are co-ordination compounds, i.e., metal The M - C bond possesses both s - and p - character.
complexes. For ex : chlorophyll is a coordination compound The M - C - bond is formed by donation of lone pair of electrons
of magnesium; haemoglobin is a complex compound of iron; from a filled bonding 2p orbital on the carbonyl carbon of CO
vitamin B12 is a co-ordination compound of cobalt, etc. into a vacant d-orbital of metal.
The M - C - bond is formed by donation of a pair of electrons
ORGANOMETALLIC COMPOUNDS
These are compounds containing one or more metal-carbon bonds. from a filled d - orbital of metal into vacant antibonding *2p orbital
The compounds of metalloids (Ge, Sb) and non metals (B, Si, P, As of CO. Here, donation of electrons from a filled metal d-orbital into
etc.) which are less electronegative than carbon are also a vacant antibonding * orbital of CO occurs, thus this bonding
categorised under this. is called back bonding.
e.g., R - Zn - R Dialkyl zinc (Frankland reagent) The effect of -bond formation strengthens the bond and vice
R - Mg - X Alkyl Mg halide (Grignards reagent) - versa. This is called synergic effect which strengthens the bond
Compounds like between CO and metal.
O
Sodium acetate CH3 - C- ONa
M C O
Sodium ethoxide C2H5–O–Na
Sodium Mercaptide H3C–SNa
are not organometallic compounds as in these compounds
metal is not directly attached with carbon atom. Synergic bonding
H3CO Synthesis of Organometallic Compounds
B(OCH3)3 is not OMC B-OCH3
(i) – bonded organometallic compounds
H3CO
R — X + 2M (CH3CH 2 )2 O R —M + MX
OCH3
R — X + Mg (CH3CH 2 )2 O R — Mg — X
while CH3B(OCH3)2 is OMC H3C - B
OCH3 SnCl4 + 4BuLi Bu4Sn + 4 LiCl
Cyanides, carbides and carbonates are not considered OMC Tetrabutyltin
because their properties are very different from those belonging
to class of OMC’s. PbCl4 4C2 H5 Br (C2 H5 )4 Pb + 4MgBrCl
Classification of Organometallic Compounds Tetraethyllead (TEL)

OMC can be classified into three main categories

(ii) K 2 [PtCl4 ] CH 2 CH 2 K[PtCl3 (C 2 H 4 )] KCl
(i) - bonded OMC : Zeise's salt
These compounds are formed mostly by non transition and
metalloid elements. 2C5 H5 MgBr + FeCl2 [(C5 H5 ) 2 Fe] + 2MgBrCl
Ferrocene
eg. R - Mg - X, (Grignard reagent)
(CH3)2Zn (Dimethyl zinc or Frankland’s reagent) Applications of Organometallic Compounds
(R)2Cd, (Dialkyl Cadmium) (i) Wilkinsons Catalyst
(ii) - bonded OMC : [RhCl(Ph3P)] is used for selective hydrogenation of alkenes.
These are usually formed by transition metals. (ii) As heterogenous catalyst
eg. Ferrocene [Fe( 5 - C5H5)2] Zeigler – Natta Catalyst is used for low temperature
polymerisation of alkenes.
where = No. of carbon atoms combined with metal atom.
(iii) Organic synthesis - OMC like R - Mg - X, R2 - Cd, CH3 - Li
Zeise’s salt K[PtCl3( 2 - C2H4)]
etc. are used for preparation of almost all type of organic
(iii) and - bonded OMC : compounds. .
Transition metals of gp. 6, 7,8,9 and 10 in their zero oxidation (iv) As petrol additive - TEL(Tetraethyl lead) is used as an
state form such type of OMC. antiknock agent in petrol.
The carbonyl compounds of these metals have both , and (v) In medicine - Organo arsenic compounds are used as medicine
bonds. e.g. for syphilis disease.
[Ni(CO)4], [Fe(CO)5], [Mn2(CO)10] (vi) In agriculture - Seeds are treated with ethyl mercury chloride
Metal carbonyls are used as industrial catalysts. They are to protect the plants against infection.
also used as precursors in synthesis of organic compounds.
 ALTITUDE CLASSES
COORDINATION COMPOUNDS

EXERCISE - 1
1. Which one of the following shows maximum value of 12. The number of ions formed when triamminetrichloro
paramagnetic behaviour : chromium (III) is dissolved in water :
(a) [Sc(CN)6]3– (b) [Co(CN)6]3– (a) 2 (b) 3
(c) [Fe(CN)6]3– (d) [Cr(CN)6]3– (c) 1 (d) None of these
13. The IUPAC name for the complex [Co(ONO)(NH3)5]Cl2 is
2. K 3[Al(C 2O 4 )3 ] is called
(a) pentaamminenitrito-N-cobalt(II) chloride
(a) Potassium aluminooxalate (b) pentaamminenitrito-N-cobalt(III) chloride
(b) Potassium trioxalatoaluminate (III) (c) nitrito-N-pentaamminecobalt(III) chloride
(c) Potassium aluminium (III) oxalate (d) nitrito-N-pentaamminecobalt(II) chloride
(d) Potassium trioxalatoaluminate (VI)
3. The formula for the complex, dichlorobis (urea) copper (II) is 14. K 4 [Fe(CN) 6 ] is a :
(a) [Cu{O = C (NH2)2}] Cl2 (a) double salt (b) complex compound
(b) [Cu{O = C (NH2)2}Cl]Cl (c) acid (d) base
(c) [CuCl2 {O = C(NH2)2}2]
15. [EDTA]4 is a :
(d) [CuCl2] [{O = C (NH2)2}]2
4. Which of the following is not an organometallic compound? (a) monodentate ligand (b) bidentate ligand
(a) sodium ethoxide (c) quadridentate ligand (d) hexadentate ligand
(b) trimethyl aluminium 16. What is incorrect about homoleptic metal carbonyls ?
(c) tetraethyl lead (a) M – C - bond is formed by donation of lone pair of
(d) ethyl magnesium bromide electrons from CO
5. The geometry of Ni(CO)4 and Ni(PPh3)2Cl2 are : (b) M – C - bond is formed by back donation of electron
(a) both square planar from filled d-orbital of metal to vacant p- orbital of carbon
(b) tetrahedral and square planar respectively (c) M – CO bonding product synergic effect
(c) both tetrahedral (d) Metal carbonyl contain only - bonds
(d) square planar and tetrahedral respectively 17. The compound having the lowest oxidation state of iron is:
6. The hypothetical complex chlorodiaquatriamminecobalt (III) (a) (b) K 2 FeO 4
K 4 Fe(CN) 6
chloride can be represented as
(a) [CoCl(NH3)3 (H2O)2]Cl2 (c) Fe 2O 3 (d) Fe(CO)5
(b) [Co(NH3)3 (H2O)Cl3] 18. The IUPAC name of K2[PtCl6] is
(c) [Co(NH2)3 (H2O)2 Cl] (a) hexachloroplatinate potassium
(d) [Co(NH3)3 (H2O)3]Cl3 (b) potassium hexachloroplatinate (IV)
7. According to IUPAC nomenclature sodium nitroprusside is (c) potassium hexachloroplatinate
named as (d) potassium hexachloroplatinum (IV)
(a) Sodium pentacyanonitrosylferrate (III) 19. In K4[Fe(CN)6], the E.A.N. of Fe is
(b) Sodium nitroferrocyanide (a) 33 (b) 35 (c) 36 (d) 26
(c) Sodium nitroferricyanide 20. The organometallic compound is :
(d) Sodium pentacyanonitrosylferrate (II)
8. In the coordination compound, K4[Ni(CN)4], the oxidation (a) Ti (OCOCH 3 ) 4 (b) Ti(C2 H5 )4
state of nickel is (c) Ti (OC 6 H 5 ) 4 (d) Ti (OC 2 H 5 ) 4
(a) 0 (b) +1 (c) +2 (d) –1
21. In [Ni(NH3)4]SO4, the E.A.N. of Ni is
9. Which does not give a precipitate with AgNO3 solution ?
(a) 34 (b) 35
(a) [Co(NH3)6] Cl3 (b) [Co(NH3)5Cl] Cl2
(c) 36 (d) 37
(c) [Co(NH3)4 Cl2] Cl (d) [Co(NH3)3Cl3]
22. The effective atomic number of cobalt in the complex
10. The oxidation state of Cr in [Cr ( NH 3 ) 4 Cl 2 ] is [Co(NH3)6]3+ is
(a) 0 (b) + 1 (c) + 2 (d) + 3 (a) 36 (b) 33 (c) 24 (d) 30
11. The IUPAC name of the coordination compound 23. The ligand called acid is :
(a) C O (b) NH3
K 3[Fe(CN ) 6 ] is
(c) C2O42– (d) Ethylenediamine
(a) Tripotassium hexacyanoiron (II) 24. Pick out the complex compound in which the central metal
(b) Potassium hexacyanoiron (II) atom obeys EAN rule strictly
(c) Potassium hexacyanoferrate (III) (a) K4[Fe(CN)6] (b) K3[Fe(CN)6]
(d) Potassium hexacyanoferrate (II) (c) [Cr(H2O)6]Cl3 (d) [Cu(NH3)4]SO4
 ALTITUDE CLASSES
CHEMISTRY
25. The number of geometrical isomers for [Pt (NH3)2 Cl2] is 36. Coordination isomerism is caused by the interchange of
(a) 2 (b) 1 (c) 3 (d) 4 ligands between the
26. Which one of the following forms, with an excess of CN– (a) cis and trans structure
(cyanide), a complex having co-ordination number two? (b) complex cation and complex anion
(a) Cu+ (b) Ag+ (c) Ni2+ (d) Al(OH)3 (c) inner sphere and outer sphere
(d) low oxidation and higher oxidation states
27. Which of the following will give maximum number of isomers? 37. The pair in which both species have same magnetic moment
(a) [Ni (C2O4) (en)2]2– (b) [Ni (en) (NH3)4]2+ (spin only value) is :
(c) [Cr (SCN)2 (NH3)4]+ (d) [Co (NH3)4 Cl2] (a) [Cr(H2O)6]2+ , [CoCI4]2–
28. Which one of the following octahedral complexes will not
show geometric isomerism? (A and B are monodentate (b) [Cr(H 2 O 6 ) 2 , [Fe(H 2 O) 6 ]2
ligands) (c) [Mn(H 2 O)6 ]2+ ,[Cr(H 2O)6 ]2+
(a) [MA5B] (b) [MA2B4]
(c) [MA3B3] (d) [MA4B2] (d) [CoCl 4 ) 2 , [Fe(H 2 O) 6 ]2
29. Which of the following coordination compounds would 38. The ligands in anti cancer drug cis-platin are:
exhibit optical isomerism? (a) NH3, CI (b) NH3, H2O
(a) pentamminenitrocobalt(III) iodide (c) Cl, H2O (d) NO, Cl
(b) diamminedichloroplatinum(II) 39. The number of precipitable halide ions in the sample
(c) trans-dicyanobis (ethylenediamine) chromium (III) [Pt(NH3)Cl2Br]Cl will be
chloride (a) 2 (b) 3 (c) 4 (d) 1
40. Wavelength of red light is absorbed by the complex
(d) tris-(ethylendiamine) cobalt (III) bromide
(a) [Cu(CN)4]2– (b) [Cu(NH3)4]2+
30. The type of isomerism present in Pentaminenitrochromium (c) CuSO4 (d) Cu(CN)2
(III) chloride is 41. Which of the following is considered to be an anticancer
(a) optical (b) linkage species ?
(c) ionisation (d) polymerisation.
31. The correct order for the wavelength of absorption in the Cl CH2 Cl Cl
visible region is : (a) Pt CH2 (b) Pt
Cl Cl Cl Cl
(a) [ Ni( NO 2 ) 6 ]4 [ Ni( NH 3 ) 6 ]2
Cl
[ Ni (H 2 O) 6 ]2 H3N
H3N Cl
(c) Pt (d) Pt
4
(b) [ Ni( NO 2 ) 6 ] [ Ni (H 2 O) 6 ]2 H3N Cl Cl NH3
2
[ Ni ( NH 3 ) 6 ]
42. Which one of the following will show paramagnetism
(c) [ Ni( H 2 O ) 6 ] 2
[ Ni( NH 3 ) 6 ] 2 corresponding to 2 unpaired electrons?
(Atomic numbers : Ni = 28, Fe = 26)
[ Ni( NO 2 ) 6 ]4 (a) [FeF6]3– (b) [NiCl4]2–
(c) [Fe (CN)6] 3– (d) [Ni (CN)4]2–
2
(d) [ Ni( NH 3 ) 6 ] [ Ni ( H 2 O) 6 ] 2 43. [Fe(NO2)3Cl3] and [Fe(ONO)3Cl3] shows
(a) linkage isomerism (b) geometrical isomerism
[ Ni( NO 2 ) 6 ]4 (c) optical isomerism (d) none of the above
32. Which of the following compounds shows optical 44. The number of unpaired electrons in the complex
isomerism? [Cr(NH3)6]Br3 is (Atomic number Cr = 24)
(a) 4 (b) 1 (c) 2 (d) 3
(a) [Co(CN) 6 ]3 (b) [Cr(C 2 O 4 )3 ]3 45. Atomic number of Cr and Fe are respectively 25 and 26,
which of the following is paramagnetic?
(c) [ ZnCl4 ]2 (d) [Cu ( NH 3 ) 4 ]2 (a) [Cr(CO)6] (b) [Fe(CO)5]
33 Which of the following ions can exhibit optical isomerism– (c) [Fe(CN)6]–4 (d) [Cr(NH3)6]+3
(a) [Co(NH3)4Cl2]+ (b) [Co(NH3)2Cl4]– 46. [Cr(H2O)6]Cl3 (at. no. of Cr = 24) has a magnetic moment of
+ 3.83 B. M. The correct distribution of 3d electrons in the
(c) Cis-[Co(en)2Cl2] (d) trans-[Co(en)2Cl2]+
Chromium of the complex is
34. Which would exhibit co-ordination isomerism
(a) [Cr(NH3)6][Co(CN)6] (b) [Co(en)2Cl2] (a) 3d 1 , (3d 2 2 )1,3d 1
xy x y yz
(c) [Cr(NH3)6]Cl3 (d) [Cr(en)2Cl2]+ (b) 3d ,3d 1 ,3d 1
xy1 yz xz
35. [Co(NH3)5NO2]Cl2 and [Co(NH3)5(ONO)]Cl2 are related to
(c) 3d , 3d ,3d
each other as xy1 yz1 z2
(a) geometrical isomers (b) optical isomers (d) (3d 1
) ,3d 2 , 3d
(c) linkage isomers (d) coordination isomers x2 y2 z xz1
 ALTITUDE CLASSES
COORDINATION COMPOUNDS
47. Which one of the following cyano complexes would exhibit (c) Co must be in +3 oxidation state
the lowest value of paramagnetic behaviour ? (d) None of these
(a) [Co(CN) 6 ]3 (b) [Fe(CN) 6 ]3 56. Which one of the following complexes is an outer orbital
complex ?
(c) [Mn (CN) 6 ]3 (d) [Cr (CN) 6 ]3 (a) [Co(NH3)6]3+ (b) [Mn(CN)6]4–
(At. Nos : Cr = 24, Mn = 25, Fe = 26, Co = 27) (c) [Fe(CN)6]4– (d) [Ni(NH3)6]2+
48. A chemist wants to determine the molecular geometry of the (Atomic nos. : Mn = 25; Fe = 26; Co = 27, Ni = 28)
[CoCl 4 ]2– ion. Which of the following gives the best 57. A square planar complex is formed by hybridisation of which
suggestion for a measurement and for the interpretation of atomic orbitals?
that measurement? (a) s, px , py , dyz (b) s, px , p y , d x 2 y 2
(a) Using absorption spectroscopy, measure max then
calculate o for octahedral geometry (c) s, px , p y , d 2 (d) s, py , pz , dxy
z
(b) Measure the molecule’s magnetic moment and use the 58. Which of the following may be considered to be an
result to estimate the number of unpaired spins in the organometallic compound?
molecule. If this number is low, the geometry is likely to be (a) Nickel tetracarbonyl (b) Chlorophyll
square planar; otherwise, it is likely to be tetrahedral (c) K3 [Fe (C2O4)3] (d) [Co (en)3] Cl3
(c) Measure the molecule’s magnetic moment and use the 59. Which of the following organometallic compound is and
result to estimate the number of unpaired spins in the bonded?
molcule.If this number is low, the geometry is likely to be (a) [Fe ( 5 – C5H5)2] (b) Fe (CH3)3
tetrahedral; otherwise, it is likely to be square planar
(c) K [PtCl3( 2 – C2H4)] (d) [Co(CO)5 NH3]2+
(d) Measure the molecule’s magnetic moment and use the
result to estimate the number of unpaired spins in the 60. In Fe2(CO)9, the two iron atoms are
molecule. If this number is low, the geometry is likely to (a) linked only directly
be tetrahedral; otherwise, it is likely to be octahedral (b) linked directly along with 3 CO molecules as bridging
49. The value of the ‘spin only’ magnetic moment for one of the ligands
following configurations is 2.84 BM. The correct one is (c) linked only through 3 CO molecules as bridging ligands
(d) joined through one CO group as bridging ligands.
(a) d 5 (in strong ligand field)
61. Among the following, which is not the -bonded
(b) d 3 (in weak as well as in strong fields) organometallic compound?
(c) d 4 (in weak ligand fields) (a) ( CH 3 ) 4 Sn (b) K [ PtCl 3 ( 2
C 2 H 4 )]
4 (c) 5 (d) 6
(d) d (in strong ligand fields) Fe ( C5 H 5 ) 2 Cr ( C6H 6 )2
50. The "spin-only" magnetic moment [in units of Bohr 62. Which one of the following is the correct order of field
magneton, (µB)] of Ni2+ in aqueous solution would be strength of ligands in spectrochemical series?
(At. No. Ni = 28)
(a) I – < Cl– < F – < H2O < CN–
(a) 6 (b) 1.73 (c) 2.84 (d) 4.90
(b) F – < H2O < I – < CN – < Cl–
51. How many pairs of enantiomers are possible for following
complex compound, [M (AB) (CD) ef]n± (c) CN – < I – < F – < Cl– < H2O
(where AB, CD– Unsymmetrical bidentate ligand, e, f– (d) H2O < F – < CN – < Cl– < I–
Monodentate ligands) 63. Which of the following does not have a metal- carbon bond?
(a) 20 (b) 5 (c) 10 (d) 8 (a) Al(OC 2 H 5 ) 3 (b) C 2 H 5MgBr
52. Which has maximum paramagnetic nature ?
(c) K[Pt (C 2 H 4 )Cl 3 ] (d) Ni(CO) 4
(a) [Mn (H 2 O) 6 ]2 (b) [Cu( NH 3 ) 4 ]2
64. Coordination compounds have great importance in biological
(c) [Fe(CN) 6 ]4 (d) [Cu(H 2 O) 4 ]2 systems. In this context which of the following statements
53. The compound which is not coloured is is incorrect ?
(a) Cyanocobalamin is B12 and contains cobalt
(a) K 4 [Fe(CN)6 ] (b) K3[Fe(CN)6 ]
(b) Haemoglobin is the red pigment of blood and contains
(c) Na 2 CdCl 4 (d) Na 2 CuCl 4 iron
2+
54. Which complex of Co will have the weakest crystal field (c) Chlorophylls are green pigments in plants and contain
splitting – calcium
(a) [CoCl6]4– (b) [Co(CN)6]4– (d) Carboxypeptidase - A is an enzyme and contains zinc.
(c) [Co(NH3)6] 2+ (d) [Co(en)3]2+ 65. Ammonia will not form complex with
55. A complex [CoL6]n+ where L is neutral ligand has a magnetic (a) Ag2+ (b) Pb2+ (c) Cu2+ (d) Cd2+
moment = 4.5 B. M. Hence, 66. In Fe(CO)5, the Fe – C bond possesses
(a) Co must be in +2 oxidation state (a) ionic character (b) -character only
(b) L must be a strong ligand
(c) -character (d) both and characters
 ALTITUDE CLASSES
CHEMISTRY
67. Which method can be used to distinguish 78. Which of the following complex ion is not expected to absorb
[Co(NH3 )6 ][Cr(NO 2 ) 6 ] and [Cr(NH3)6][Co(NO2)6] visible light ?
2 3
(a) by measurement of their conductivity (a) Ni(CN)4 (b) Cr(NH3 )6
(b) by titration method
(c) by precipitation method with AgNO3 2 2
(c) Fe(H 2 O)6 (d) Ni(H 2O)6
(d) by electrolysis of their aqueous solutions
79. Which one of the following complexes is not expected to
68. The organometallic compound is :
exhibit isomerism?
(a) Ti (OCOCH 3 ) 4 (b) Ti (C 2 H 4 ) 4
2 2
(c) Ti (OC 6 H 5 ) 4 (d) Ti (OC 2 H 5 ) 4 (a) Ni(en)3 (b) Ni NH3 4
H 2O 2
69. Which of the following is an organometallic compound?
(a) Lithium methoxide (c) Pt NH3 2
Cl 2 (d) Ni NH3 2
Cl 2
(b) Lithium acetate 80. Of the following complex ions, which is diamagnetic in
(c) Lithium dimethylamide nature?
(d) Methyl lithium
(a) [NiCl4]2– (b) [Ni(CN)4]2–
70. The formula of ferrocene is 2–
(c) [CuCl4] (d) [CoF6]3–
(a) [Fe(CN)6]4– (b) [Fe(CN)6]3–
81. The complexes [Co(NH3)6] [Cr(CN)6 ] and [Cr(NH3 )6 ]
(c) [Fe(CO)5] (d) [(C5H5)2Fe]
[Co(CN)6] are the examples of which type of isomerism?
71. The – bonded organometallic compound which has ethene
(a) Linkage isomerism
as one of its component is
(b) Ionization isomerism
(a) Zeise’s salt (b) Ferrocene
(c) Coordination isomerism
(c) Dibenzene chromium (d) Tetraethyl tin
72. Which of the following will give a pair of enantiomorphs? (d) Geometrical isomerism
(a) [Cr(NH3)6][Co(CN)6] 82. The complex, [Pt(py)(NH3 )BrCl] will have how many
(b) [Co(en)2Cl2]Cl geometrical isomers ?
(c) [Pt(NH3)4] [PtCl6] (a) 3 (b) 4 (c) 0 (d) 2
(d) [Co(NH3)4Cl2]NO2. (en =NH2CH2CH2NH2) 83. Which of the following complex compounds will exhibit
73. The d electron configurations of Cr 2+, Mn2+, Fe2+ and Ni2+ highest paramagnetic behaviour?
are 3d 4, 3d 5, 3d 6 and 3d 8 respectively. Which one of the (At. No. : Ti = 22, Cr = 24, Co = 27, Zn = 30)
following aqua complexes will exhibit the minimum (a) [Ti (NH3)6]3+ (b) [Cr (NH3)6]3+
(c) [Co (NH3)6] 3+ (d) [Zn (NH3)6]2+
paramagnetic behaviour?
(a) [Fe(H2O)6]2+ (b) [Ni(H2O)6]2+ 84. Red precipitate is obtained when ethanol solution of
(c) [Cr(H2O)6] 2+ (d) [Mn(H2O)6]2+ dimethylglyoxime is added to ammoniacal Ni(II). Which of
(At. No. Cr = 24, Mn = 25, Fe = 26, Ni = 28) the following statements is not true ?
74. Which of the following complexes exhibits the highest (a) Red complex has a square planar geometry.
paramagnetic behaviour ? (b) Complex has symmetrical H-bonding
(a) [V(gly)2(OH)2(NH3)2]+ (c) Red complex has a tetrahedral geometry.
(b) [Fe(en)(bpy)(NH3)2]2+ (d) Dimethylglyoxime functions as bidentate ligand.
(c) [Co(ox)2(OH)2]2–
(d) [Ti(NH3)6]3+ OH
H3C C N
where gly = glycine, en = ethylenediamine and bpy = dimethylglyoxime =
bipyridyl moities) H3C C N
(At.nosTi = 22, V = 23, Fe = 26, Co = 27) OH
75. In which of the following coordination entities the magnitude 85. Low spin complex of d 6 -cation in an octahedral field will
0 (CFSE in octahedral field) will be maximum? have the following energy :
(a) [Co(H2O)6]3+ (b) [Co(NH3)6]3+
(c) [Co(CN)6] 3– (d) [Co (C2O4)3]3– 12 12
(a) 0 P (b) 0 3P
(At. No. Co = 27) 5 5
76. Which of the following does not show optical isomerism?
2 2
(a) [Co(NH3)3Cl3]0 (b) [Co (en) Cl2 (NH3)2]+ (c) 0 2P (d) 0 P
(c) [Co (en)3] 3+ (d) [Co (en)2Cl2]+ 5 5
(en = ethylenediamine) ( 0= Crystal Field Splitting Energy in an octahedral field,
77. Which of the following complex ions is expected to absorb P = Electron pairing energy)
visible light? 86. Which of the following has a square planar geometry?
(a) [Ti (en)2(NH3)2]4 + (b) [Cr (NH3)6]3 + (a) [PtCl4]2– (b) [CoCl4]2–
(c) [FeCl4] 2– (d) [NiCl4]2–
(c) [Zn (NH3)6]2 + (d) [Sc (H2O)3 (NH3)3]3+
(At. no. Zn = 30, Sc = 21, Ti = 22, Cr = 24) (At. nos.: Fe = 26, Co = 27, Ni = 28, Pt = 78)
 ALTITUDE CLASSES
COORDINATION COMPOUNDS
87. The coordination number and the oxidation state of the 92. Which of the following facts about the complex
element ‘E’ in the complex [Cr(NH3)6]Cl3 is wrong?
[E (en)2 (C2O4)]NO2 (where (en) is ethylene diamine) are, (a) The complex involves d 2 sp3 hybridisation and is
respectively, octahedral in shape.
(a) 6 and 2 (b) 4 and 2 (b) The complex is paramagnetic.
(c) 4 and 3 (d) 6 and 3 (c) The complex is an outer orbital complex
88. Which of the following pairs represent linkage isomers? (d) The complex gives white precipitate with silver nitrate
solution.
(a) [Pd(PPh3)2(NCS)2] and [Pd ( PPh3)2 (SCN)2]
93. Among the ligands NH3, en, CN– and CO the correct order
(b) [Co(NH3)5NO3] SO4 and [Co(NH3)5SO4]NO3
of their increasing field strength, is :
(c) [PtCl2(NH3)4] Br2 and [Pt Br 2 (NH3)4] Cl2
(d) [Cu(NH3)4][Pt Cl4] and [Pt(NH3)4][CuCl4] (a) NH3 en CN CO
89. A solution containing 2.675 g of CoCl3. 6 NH3 (molar mass =
(b) CN NH3 CO en
267.5 g mol–1) is passed through a cation exchanger. The
chloride ions obtained in solution were treated with excess
(c) en CN NH3 CO
of AgNO3 to give 4.78 g of AgCl (molar mass = 143.5 g mol–
1). The formula of the complex is
(d) CO NH3 en CN
(At. mass of Ag = 108 u)
94. Which among the following will be named as dibromidobis
(a) [Co(NH3 )6 ]Cl3 (b) [CoCl2 (NH3 )4 ]Cl (ethylene diamine) chromium (III) bromide?
(c) [CoCl3 (NH3 )3 ] (d) [CoCl(NH3 )5 ]Cl2 (a) [Cr (en)3]Br3 (b) [Cr(en)2Br2]Br
(c) [Cr(en)Br4] – (d) [Cr(en)Br2]Br
90. Which one of the following has an optical isomer?
95. As per IUPAC nomenclature, the name of the complex
(a) [Zn(en) (NH3)2]2+ (b) [Co(en)3]3+
[Co(H2O)4(NH3)2]Cl3 is :
(c) [Co(H2O)4(en)]3+ (d) [Zn(en)2]2+
(a) Tetraaquadiaminecobalt (III) chloride
(en = ethylenediamine)
(b) Tetraaquadiamminecobalt (III) chloride
91. Which one of the following complex ions has geometrical
(c) Diaminetetraaquacoblat (II) chloride
isomers ?
(d) Diamminetetraaquacobalt (III) chloride
(a) [Ni(NH3)5Br]+ (b) [Co(NH3)2(en)2]3+
(c) [Cr(NH3)4(en)2]3+ (d) [Co(en)3]3+
(en = ethylenediamine)
 ALTITUDE CLASSES
CHEMISTRY

EXERCISE - 2
1. The crystal field splitting energy for octahedral ( 0) and (a) Diamminedichloroplatinum (II)
tetrahedral ( t) complexes is related as (b) Tetraamminedichlorocobalt (III) chloride
(c) Potassium hexacyanoferrate (II)
1 4
(a) t – 0 (b) t – 0 (d) Hexaaquochromium (III) chloride
2 9
9. One mole of the complex compound Co(NH3)5Cl3, gives 3
3 2 moles of ions on dissolution in water. One mole of the same
(c) t – 0 (d) t – 0
5 5 complex reacts with two moles of AgNO3 solution to yield
2. Among the following complexes, optical activity is possible two moles of AgCl (s). The structure of the complex is
in (a) [Co(NH3)3Cl3]. 2 NH3 (b) [Co(NH3)4Cl2] Cl . NH3
(c) [Co(NH3)4Cl] Cl2. NH3 (d) [Co(NH3)5Cl] Cl2
(a) [ Co ( NH 3 ) 6 ]3
10. The ligand N(CH2CH2NH2)3 is
(b) [ Co ( H 2 O) 2 ( NH 3 ) 2 Cl 2 ] (a) tridentate (b) pentadentate
(c) (c) tetradentate (d) bidentate
[ Cr ( H 2 O) 2 Cl 2 ]
11. Among the properties (a) reducing (b) oxidising (c)
(d) [ Co ( CN ) 5 NC ] complexing, the set of properties shown by CN– ion towards
3. Facial and meridional isomerism will be exhibited by metal species is
(a) [Co(NH3)3Cl3] (b) [Co(NH3)4Cl2]Cl (a) c, a (b) b, c (c) a, b (d) a, b, c
(c) [Co(en)3]Cl3 (d) [Co(NH3)5Cl]Cl2 12. Which one of the following has largest number of isomers ?
4. A co-ordination complex compound of cobalt has the
molecular formula containing five ammonia molecules, one (a) [Ir(PR 3 ) 2 H(CO)]2
nitro group and two chlorine atoms for one cobalt atom. One (b) [Co( NH3 )5 Cl]2
mole of this compound produces three mole ions in an
aqueous solution. On reacting this solution with excess of (c) [Ru( NH3 ) 4 Cl2 ]
AgNO3 solution, we get two moles of AgCl precipitate. The (d) [Co(en ) 2 Cl 2 ] (R = alkyl group, en = ethylenediamine)
ionic formula for this complex would be 13. Which among the following statements are true for the
(a) [Co(NH3)4 (NO2) Cl] [(NH3) Cl] complex [Co(NH3)6][Cr(CN)6] ?
(b) [Co (NH3)5 Cl] [Cl (NO2)] 1. It is a non-electrolyte
(c) [Co (NH3)5 (NO2)] Cl2
2. The magnitude of the charge on each complex ion is 3
(d) [Co (NH3)5] [(NO2)2Cl2]
3. The complex will not conduct current
5. Which of the following complexes exists as pair of
4. The complex will exhibit coordination isomerism
enantiomers?
5. The magnitude of the charge on each complex ion is 1
(a) trans-[Co(en)2Cl2]+
(a) 1 and 4 (b) 1 and 2
(b) [Co(NH3)4Cl2]+
(c) 1 and 3 (d) 2 and 4
(c) [Co{P(C2H5)3}2ClBr]
14. The correct order of magnetic moments (spin only values in
(d) [Cr(en)3]+3
B.M.) among is
6. Which one of the following is an inner orbital complex as
well as diamagnetic in behaviour? (Atomic number: (a) [ Fe (CN ) 6 ]4 [ MnCl 4 ] 2 [CoCl 4 ] 2
Zn = 30, Cr = 24, Co = 27, Ni = 28) (b) [ MnCl 4 ] 2 [ Fe (CN ) 6 ] 4 [CoCl 4 ] 2
(a) [Zn(NH3 )6]2+ (b) [Cr(NH3)6]3+
(c) [Co(NH3)6] 3+ (d) [Ni(NH3)6]2+ (c) [MnCl 4 ]2 [CoCl 4 ]2 [Fe(CN ) 6 ]4
7. [Co(NH3)4 (NO2)2] Cl exhibits
(d) [ Fe (CN ) 6 ]4 [CoCl 4 ]2 [ MnCl 4 ] 2
(a) linkage isomerism, ionization isomerism and geometrical
isomerism (Atomic nos. : Mn = 25, Fe = 26, Co = 27)
(b) ionization isomerism, geometrical isomerism and optical 15. Among the following coordination compounds/ions
isomerism 3
(i) Fe CN 6 (ii) Pt NH3 2 Cl 2
(c) linkage isomerism, geometrical isomerism and optical
isomerism 3
(iii) Co NH 3 6 (iv) Cr H 2 O 6 Cl3
(d) linkage isomerism, ionization isomerism and optical
isomerism Which species exhibit geometrical isomerism?
8. Which one of the following has the highest molar (a) (ii) only (b) (i) and (ii)
conductivity? (c) (ii) and (iv) (d) (i) and (iii)
 ALTITUDE CLASSES
COORDINATION COMPOUNDS
16. Nickel (Z = 28) combines with a uninegative monodentate 24. Which of the following carbonyls will have the strongest
ligand X– to form a paramagnetic complex [NiX4]2–. The C – O bond ?
number of unpaired electron(s) in the nickel and geometry (a) [Mn (CO)6]+ (b) [Cr (CO)6]
of this complex ion are, respectively (c) [V (CO)6]– (d) [Fe (CO)5]
(a) one, square planar (b) two, square planar 25. Which one of the following is an outer orbital complex and
(c) one, tetrahedral (d) two, tetrahedral exhibits paramagnetic behaviour ?
17. A complex cation is formed by Pt (in some oxidation state) (a) [Ni(NH3)6]2+ (b) [Zn(NH3)6)]2+
with ligands (in proper number so that coordination number (c) [Cr(NH3)6] 3+ (d) [Co(NH3)6]3+
of Pt becomes six). Which of the following can be its correct 26. In which of the following complexes of the Co (at. no. 27),
IUPAC name ? will the magnitude of o be the hightest?
(a) Diammineethylenediaminedithiocyanato-S-platinum (II) (a) [Co(CN)6]3– (b) [Co(C2O4)3]3–
(c) [Co(H2O)6] 3+ (d) [Co(NH3)6]3+
(b) Diammineethylenediaminedithiocyanato-S-platinate
(IV) ion 27. Which of the following has an optical isomer
(c) Diammineethylenediaminedithiocyanato-S-platinum (a) [Co(en) (NH3)2]2+ (b) [Co(H2O)4(en)]3+
(c) [Co(en)2 (NH3)2] 3+ (d) [Co(NH3)3Cl] +
(IV) ion
(d) Diamminebis (ethylenediamine) dithiocyanato-S-plati- 28. Among the following metal carbonyls, the C–O bond order
num (IV) ion is lowest in
(a) [Mn(CO)6]+ (b) [Fe(CO)5]
18. [Fe(en)2 (H2 O)2 ]2+ + en complex (X). The correct
(c) [Cr(CO)6] (d) [V(CO)6]–
statement about the complex (X) is –
29. The IUPAC name of [Ni (NH3)4] [NiCl4] is
(a) it is a low spin complex
(a) Tetrachloronickel (II) - tetraamminenickel (II)
(b) it is diamagnetic
(b) Tetraamminenickel (II) - tetrachloronickel (II)
(c) it shows geometrical isomerism (c) Tetraamminenickel (II) - tetrachloronickelate (II)
(d) (a) and (b) both (d) Tetrachloronickel (II) - tetrachloronickelate (0)
19. Among the following, the species that is both paramagnetic 30. Both [Ni(CO)4] and [Ni(CN)4]2– are diamagnetic. The
and coloured is – hybridisations of nickel in these complexes, respectively,
(a) [MnO4]2– (b) [TiCl6]2– are
(c) [VO4]3– (d) CrO2Cl2 (a) sp3, sp3 (b) sp3, dsp2(c) dsp2, sp3 (d) dsp2, sp2
20. 0.02 mole of [Co(NH 3 ) 5 Br]Cl 2 and 0.02 mole of 31. The spin only magnetic moment value (in Bohr magneton
units) of Cr(CO)6 is
[Co(NH3)5Cl]SO4 are present in 200 cc of a solution X. The
(a) 0 (b) 2.84 (c) 4.90 (d) 5.92
number of moles of the precipitates Y and Z that are formed
32. The ionisation isomer of [Cr(H2O)4Cl(NO2)]Cl is
when the solution X is treated with excess silver nitrate and (a) [Cr(H2O)4(O2N)]Cl2
excess barium chloride are respectively (b) [Cr(H2O)4Cl2](NO2)
(a) 0.02, 0.02 (b) 0.01, 0.02 (c) [Cr(H2O)4Cl(ONO)]Cl
(c) 0.02, 0.04 (d) 0.04, 0.02 (d) [Cr(H2O)4Cl2(NO2)].H2O
33. The correct structure of ethylenediaminetetraacetic acid
21. Crystal field stabilization energy for high spin d 4 octahedral
(EDTA) is
complex is:
HOOC – H2C CH2– COOH
(a) – 1.8 (b) – 1.6 0 + P (a) N – CH = CH – N
0
HOOC – H2C CH2– COOH
(c) – 1.2 0 (d) – 0.6 0 HOOC COOH
22. The existence of two different coloured complexes with the (b) N – CH2 – CH2 – N
HOOC COOH
+
composition of [Co(NH3 )4 Cl2 ] is due to : HOOC–H2C CH2–COOH
(c) N – CH2 – CH2 – N
(a) linkage isomerism (b) geometrical isomerism HOOC–H2C CH2–COOH
(c) coordination isomerism(d) ionization isomerism
COOH
23. The d-electron configurations of Cr2+, Mn2+, Fe2+ and Co2+ CH2
are d 4 , d 5, d 6 and d 7, respectively. Which one of the (d) HOOC–H2C H
following will exhibit minimum paramagnetic behaviour? N–CH–CH–N
H CH2–COOH
(a) [Mn(H2O)6]2+ (b) [Fe(H2O)6]2+ CH2
(c) [Co(H2O)6] 2+ (d) [Cr(H2O)6]2+ HOOC
(At, nos. Cr = 24, Mn = 25, Fe = 26, Co = 27)
 ALTITUDE CLASSES
CHEMISTRY
34. The complex showing a spin-only magnetic moment of 39. The compound N is
2.82 B.M. is : (a) AgNO3 (b) Zn(NO3)2
(a) Ni(CO)4 (b) [NiCl4]2– (c) Al(NO3)3 (d) Pb(NO3)2
(c) Ni(PPh3)4 (d) [Ni(CN)4]2– 40. The final solution contains
35. Among the following complexes (K P) 2 2
(a) Pb(NH 3 ) 4 and CoCl4
K3[Fe(CN)6] (K), [Co(NH3)6]Cl3 (L), Na3[Co(oxalate)3] (M),
[Ni(H2O)6]Cl2 (N), K2[Pt(CN)4] (O) and [Zn(H2O)6](NO3)2 (P) 3 2
(b) Al(NH3 )4 and Cu(NH3 )4
the diamagnetic complexes are
2
(a) K, L, M, N (b) K, M, O, P (c) Ag(NH3 )2 and Cu(NH3 )4
(c) L, M, O, P (d) L, M, N, O 2
36. [NiCl2 {P(C2H5)2(C6H5)}2] exhibits temperature dependent (d) Ag(NH3 )2 and Ni(NH3 )6
magnetic behaviour (paramagnetic/diamagnetic). The DIRECTIONS for Qs. 41 to 43 : These are Assertion-Reason
coordination geometries of Ni2+ in the paramagnetic and type questions. Each of these question contains two statements:
diamagnetic states are respectively Statement-1 (Assertion) and Statement-2 (Reason). Answer these
(a) tetrahedral and tetrahedral questions from the following four options.
(b) square planar and square planar (a) Statement-1 is True, Statement-2 is True, Statement-2 is a
(c) tetrahedral and square planar correct explanation for Statement-1
(d) square planar and tetrahedral (b) Statement-1 is True, Statement-2 is True ; Statement-2 is
37. Which of the following complex species is not expected to NOT a correct explanation for Statement-1
exhibit optical isomerism ? (c) Statement-1 is True, Statement-2 is False
(a) [Co(en)3]3+ (b) [Co(en)2 Cl2]+ (d) Statement-1 is False, Statement-2 is True
(c) [Co(NH3)3 Cl3] (d) [Co(en) (NH3)2 Cl2]+ 41. Statement-1 : NF3 is a weaker ligand than N(CH3)3.
DIRECTIONS for Qs. 38 to 40 : Read the passage given below Statement-2 : NF3 ionizes to give F– ions in aqueous
and answer the questions that follow : solution.
When a metal rod M is dipped into an aqueous colourless 42. Statement-1 : [Fe(CN)6]3– is weakly paramagnetic while
concentrated solution of compound N, the solution turns light [Fe(CN)6]4– is diamagnetic.
blue. Addition of aqueous NaCl to the blue solution gives a white Statement-2 : [Fe(CN)6]3– has +3 oxidation state while
precipitate O. Addition of aqueous NH3 dissolves O and gives an [Fe(CN)6]4– has +2 oxidation state.
intense blue solution. 43. Statement-1 : [Ti(H2O)6]3+ is coloured while [Sc(H2O)6]3+
38. The metal rod M is is colourless.
(a) Fe (b) Cu (c) Ni (d) Co Statement-1 : d-d transition is not possible in [Sc(H2O)6]3+.
 ALTITUDE CLASSES
COORDINATION COMPOUNDS

HINTS & SOLUTIONS

EXERCISE - 1 9. (d) In [Co(NH3)3Cl3], all chlorine atoms are inside the co-
ordination sphere so they will not ionise and this com-
1. (c) CN– is a strong ligand so it forces the electrons to pair pound will not give precipitate with AgNO3.
up.
10. (d) Oxidation state of Cr in [Cr ( NH 3 ) 4 Cl 2 ] .
Sc3+ Let it be x, 1 × x + 4 × 0 + 2 × (–1) = 1 Therefore x =3.
3d 4s 11. (c) K 3[Fe(CN ) 6 ] is Potassium hexacyanoferrate (III).
Cr3+ 12. (d) The given complex is [Cr(NH3)3Cl3]3+. When it is
dissolved in water it forms none other ion.
Fe3+ 13. (b) [Co(ONO)(NH3)5]Cl2
pentaamminenitrito-N-cobalt (III) chloride
Co3+ 14. (b) Complex compounds do not dissociate into constituent
4s ions.
In Sc3+, no electron is there in d orbital, in Cr 3+ one
electron is unpaired. In Fe3+ also one electron is K4[Fe(CN)6] 4K+ + [Fe(CN6)]4–
unpaired, Co3+ has no unpaired electrons. As both Cr 3+ It is a complex because no CN– is formed on
dissociation.
and Fe3+ contain one electron in unpaired state so both
15. (d) [EDTA]4– is a hexadentate ligand, because it has six
may be paramagnetic. But as we know Fe has more donor atoms and donate 6 pairs of electrons to central
magnetic properly. Fe3+ will be more paramagnetic. So metal atom in the complex.
option (c) is correct. 16. (c) It is incorrect statement.
2. (b) IUPAC name is Potassium trioxalatoaluminate (III). All other statements i.e. (a), (b) and (d) are correct.
3. (c) [CuCl2{(O = C(NH2)2}2] 17. (d) In Fe(CO)5, Fe is in minimum oxidation state (zero).
4. (a) Sodium ethoxide is not an organometallic compound 18. (b) K2[Pt Cl6]
as in this compound carbon is not directly attached Potassium hexachloroplatinate (IV)
with metal. Oxidation state of Pt is + 4 in the complex and anion is
5. (b) Both are tetrahedral. CO is a strong ligand and P(Ph 3) present in form of complex.
is a weak ligend. So, CO pair up electrons while P(PH3) 19. (c) EAN = Atomic number – Oxidation state + 2 × number
do not pair up. Oxidation state of Ni is zero in carboxyl of Ligands = 26 – 2 + 2 (6) = 36.
compound which in other Ni has + 2 oxidation state. 20. (b) Organo-metallic compound is (b) as it contains metal-
Ni(28) carbon bonds. In others, direct link of carbon with metal
is not present.
21. (a) EAN = (atomic no) – (oxidation state) + (2 × number of
Ligands) = 28 – 2 + 2 × 4 = 34
22. (a) EAN = at. no. of central atom – oxidation state + 2 ×
(no. of ligands) = 27 – 3 + 2 × 6 = 36.
sp 3 hybridised
23. (a) Due to back bonding present between metal and
Shape is tetrahedral. carbonyl ligand in metal carbonyl, CO is termed as -
Ni2+ acid ligand.
24. (a) In complex K4[Fe(CN)6] the Fe obey EAN rule strictly.
As in this complex EAN of Fe is 36, which corresponds
sp 3 hybridised to the atomic number of krypton
Hence, according to sidwick the complex will be stable
Shape is tetrahedral. 25. (a) Pt (NH3)2 Cl2 is a disubstituted complex and shows
6. (a) Chlorodiaquatriamminecobalt (III) chloride is only cis-& trans-isomers
[CoCl( NH 3 )3 (H 2O) 2 ]Cl 2 . Cl NH3 NH3 Cl
7. (a) IUPAC name of sodium nitroprusside Na2[Fe(CN)5NO]
is sodium pentacyanonitrosylferrate (III) because in it Pt Pt
NO is neutral ligand. Hence Cl
Cl NH3 NH3
2×O.N. of Na + O.N. of Fe + 5×O.N. of CN cis trans
1×O.N. of NO = 0 26. (b) Among the given metal ions only Ag+ forms complex
2×(+1) + O.N. of Fe + 5 ×(–1) +1×0 = 0 with CN– having co-ordination number 2.
O.N. of Fe = 5 – 2 = +3, Hence ferrate (III) Ag + 2CN – [Ag(CN)2 ]–
8. (a) Let the O. No. of Ni in K4[Ni(CN)4] be = x then
Coordination number of metals is defined as the number
4 (+ 1) + x + (–1) × 4 = 0 4+x–4=0 of bonds by which ligands are attached to the metal
x=0 atom.
 ALTITUDE CLASSES
CHEMISTRY
in first one and nitrogen in second, so they show
27. (c) [Cr(SCN ) 2 ( NH 3 ) 4 ] shows linkage, geometrical and linkage isomerism.
optical isomerism. Hence produces maximum no. of 36. (b) Co-ordination isomerism is caused by the interchange
isomers. of ligands between cation and anion complexes.
28. (a) MA3B3 – 2 geometrical isomers 37. (b) [Cr(H2O)6]2+. Here Cr is in Cr2+ form
MA2B4 – 2 geometrical isomers
MA4B2 – 2 geometrical isomers
The complexes of general formula MA6 and MA5B Cr 2
having octahedral geometry do not show geometrical 3d 4s
isomerism.
29. (d) The optical isomers are pair of molecules which are Fe 2
non superimposable mirror images of each other. 3d 4s
In [Fe(H2 O)]2+, 2+
Fe is in Fe form. Both will have 4
en en unpaired electrons.
38. (a) The ligands in cis-platin [PtCl2(NH3)2] are Cl and NH3.
39. (d) [Pt(NH3 )Cl2 Br]Cl [Pt(NH3 )Cl 2 Br]+ + Cl-
en Co Co en
Cl– ion is precipitable.
40. (b) The compound which appears blue green, absorb red
en en light as blue-green is complementary to red colour.
Here [Cu(NH3)4]2+ appears blue-green, so it absorbs
[Co(en)3]3+ [Co(en)3]3+ red colour.
Mirror
(dextro) (laevo) 41. (c) Diaminodichloroplatinum (II) commonly known as cis -
platin is found to have anticancer property.
The two optically active isomers are collectivity called 42. (b) As in [NiCl4]–2 Chloride ion being a weak ligand is not
enantiomers. able to pair the electrons in d orbital.
30. (b) The chemical formula of Pentaminenitrochromium (III) 43. (a) The given compound contains –NO2 group which can
chloride is donate electrons either from O– or from N– . Thus, it
Cr NH3 NO 2 Cl2 shows linkage isomerism. Thus the two given
5
compounds are linkage isomers, one is nitrite –O–N =
It can exist in following two structures
O
Cr NH3 5 NO2 Cl2 and O form and the other is nitro, –N form.
O
Cr NH3 5 ONO Cl2 44. (d) In [Cr (NH3)6]Br3, Cr is in +3 oxidation state
Therefore the type of isomerism found in this compound 3d 4s 4p
is linkage isomerism as nitro group is linked through N Cr
24
as –NO2 or through O as – ONO.
31. (a) For any metal cation, the magnitude of 0 depends d2sp3 hybridized
upon the nature of ligand. Higher the value of 0, lower 3d 4s 4p
will be the wave length absorbed. 0 is crystal field Cr
+3
stabilisation energy. 21
The value of 0 for ligands varies as follows Its ion is octahedral in nature. Due to the presence of
H 2 O NH3 NO2 three unpaired electrons it is paramagnetic.
45. (d) Cr 3+ has 4so 3d3 electronic configuration with 3
So, the wavelength absorbed will vary in reverse order unpaired electrons, hence paramagnetic. In other cases
or NO 2 NH 3 H 2 O pairing of d-electrons take place in presence of strong
32. (b) field ligands such as CO or CN–.
33. (c) cis-[Co(en)2Cl 2]+: cis-[M(aa)2b2] can show optical In Cr(CO)6 molecule 12 electrons are contributed by
isomerism. CO group and it contain no odd electron
34. (a) 46. (b) n(n 2)
35. (c) NH3 NH3 3.83 n(n 2)
H3N ONO H3N NO2 on solving n = 3
Co Co
as per magnetic moment, it has three unpaired electron.
H3N NH3 H3N NH3
Cr3+ will have configuration as
NH3 NH3
Cr 1s2 2s2 2p6 3s2 3p6 3d 4 4s2
Here more than one atom function as donor, as oxygen Cr3+ 1s2 2s2 2p6 3s2 3p6 3d 3
 ALTITUDE CLASSES
COORDINATION COMPOUNDS
52. (a) Paramagnetic species has unpaired electron. More the
no. of unpaired electrons, more will be paramagnetic
character.
dxy dyz dzx
Complex O. S. of metal
So, 3dxy1, 3dyz1, 3dxz1 2
Mn H 2 O 6
Mn 2+
47. (a) Co3+ :
2
[Co(CN)6]3– : Cu NH3 4
Cu2+
CN– is a strong field ligand and it causes pairing of
4
electrons as a result number of unpaired electrons in Fe CN Fe2+
6
Co3+ becomes zero and hence it has lowest value of
paramagnetic behaviour. 2
48. (b) In the complexes of C.N. 4, square planar geometry gives Cu H 2 O 4
Cu2+
rise to low spin (spin paired) configurations whereas Electronic configuration of the ion present in complex
tetrahedral complexes display high spin configurations. 3d 4s 4p
49. (d) d 5 –––– strong ligand field Mn2+

No. of unpaired electron = 5

t2g eg
Cu2+
= n(n 2) = 3 = 1.73BM
No. of unpaired electron = 1
d 3–– in weak as well as in strong field
Fe2+

t2g eg However, CN– is a strong ligand, so pairing of electrons

will occur in the complex having CN– ions.
= 3(5) = 15 = 3.87 B.M. Fe2+ in presence of CN–
d 4– in weak ligand field
No. of unpaired electron = 0
t2g eg Thus [Mn (H2O)6]2+ having maximum no. of unpaired
electrons has maximum paramagnetic nature.
= 4(4+2) = 24 = 4.89 53. (c) In Na2[CdCl4], Cd has oxidation state +2.
d 4– in
strong ligand field So, its electronic configuration is 4d105s0
or all the 4d orbitals are fully filled.
Hence, there will be no d-d transition. So, it is colourless.
t2g eg 54. (a) Cl– is a weak field ligand.
55. (c) Co must be in +3 oxidation state and the ligand L should
= 2(4) = 8 = 2.82.
be a weak ligand.
50. (c) The number of unpaired electrons in Ni2+(aq) = 2
Water is weak ligand hence no pairing will take place Co3+ = [Ar]3d6
spin magnetic moment n(n 2) 2(2 2) n = 4, = 4.5 BM.
8 2.83 56. (d) Hybridisation
51. (c) [Fe(CN)6 ]4 ,[Mn(CN)6 ]4 ,
e e f f d 2 sp3 d 2 sp3
A f A f A e A e
M M M M
B D B C B D B C
[Co(NH 3 ] 3 ,[Ni(NH 3 ) 6 ] 2
C D C D d 2 sp 3 sp 3d 2
e
Hence [ Ni( NH 3 ) 6 ]2 is outer orbital complex.
e f f
B f B f B e B e
M M M M 57. (b) A square planar complex is formed by hybridisation of
A D A C A D A C
s, px, py and d atomic orbitals.
C D C D x2 y 2
e e
C A D
58. (b) Organometallic compounds are those compounds in
A
M M which a metal is bonded directly to a carbon atom of a
B D B C molecule. In chlorophyll there is bond involving
f f metal Mg
 ALTITUDE CLASSES
CHEMISTRY
59. (d) [Co(CO) 5 NH 3 ]2 . In this complex Co-atom attached
71. (a)
with NH3 through bonding and with CO with dative H –
-bond.
C H
Cl
O C H K+ Fe
O C O Pt
C C H
Fe Cl Cl
Ferrocene
60. (b) O=C O=C C=O Zeise’s salt
Fe
C
O C C O (C2H5)4Sn
O tetraethyl tin
Cr
61. (a) The number of carbon atom found in bonded
organometallic compounds is indicated by the greek
letter ' ' with a number. The prefixes 2, 5 and 6
indicate that 2, 5 and 6 carbon atom are bound to the dibenzene chromium
metal in the compound.(CH3)4Sn does not involve any
pi ( ) bond formation. This is a bonded organometallic 72. (b) Non superimposable mirror images are called optical
compound. isomers and may be described as “chiral’. They are
62. (a) also called enantiomers and rotate plane polarised light
63. (a) Triethoxyaluminium has no Al – C linkage in opposite directions.
O CH 2 CH 3 Cl Cl
Al O CH 2 CH 3 Cl Cl
O CH 2 CH 3
en Co Co en
64. (c) The chlorophyll molecule plays an important role in
photosynthesis, contain porphyrin ring and the metal
Mg not Ca.
65. (b) The complex formation is a characteristic of d-block elements. en en
Lead is a p-block element hence does not forms complex 73. (b) Lesser is the number of unpaired electrons smaller will
compounds.
be the paramagnetic behaviour. As Cr ++, Mn++, Fe++
66. (d) Due to some backbonding by sidewise overlapping and Ni++ contains.
between d-orbitals of metal and p-orbital of carbon, the
Fe–C bond in Fe(CO)5 has both and character. Cr++ (3d 4) =
67. (d) In one case, on electrolysis of aqueous solution, the
= 4 unpaired e–.
complex ion of cobalt [i.e., {Co(NH3)6}3+] of the complex
[Co(NH3)6][Cr(NO2)6] moves towards cathode (i.e., Mn++ (3d 5)=
negative electrode) and on this electrode finally cobalt
would be deposited. = 5 unpaired e–.
In another case, on electrolysis of aqueous solution,
Fe++ (3d 6) =
the complex ion of chromium
[i.e., {Cr(NH 3 ) 6 } 3+ ] of the complex = 4 unpaired e–.
[Cr(NH3)6][Co(NO2)6] moves towards cathode (i.e.,
negative electrode) and on this electrode chromium Ni++ (3d 8) =
would finally be deposited. = 2 unpaired e–.
68. (b) Organometallic compound is (b) as it contains metal- As Ni++ has minimum no. of unpaired e– thus this is
carbon bonds. In others, direct link of carbon with metal least paramagnetic.
is not present. 74. (c)
69. (d) Compounds that contain atleast one carbon metal bond 75. (c) In octahedral field the crystal field splitting of d- orbitals
are called organometallic compound. Hence, based on of a metal ion depends upon the field produced by the
above definition methyl lithium is an organometallic ligands. In general ligands can be arranged in a series
compound. In other chemical compounds carbon is not in the order of increasing fields and splittings which
linked with metal. they produce around a central metal ion. A portion of
70. (d) the series is given below.
 ALTITUDE CLASSES
COORDINATION COMPOUNDS
cyanide > ethylene - diamine > ammonia > pyridine > 81. (c) Coordination isomerism occurs when cationic and
thiocyanate > water > oxalate > hydroxide > fluoride > anionic complexes of different metal ions are present in
chloride > bromide > iodide. a salt. The two isomers differ in the distribution of
Out of the given ligands water, ammonia, cyanide and ligands in cation and anion e.g.,
oxalate, we can find from the above series of ligands that [Co (NH3)6] [Cr (CN)6] is an isomer of [Co (CN)6]
the maximum splitting will occur in case of cyanide (CN–) [Cr (NH3)6]
i.e. the magnitude of 0 will be maximum in case of 82. (a) Complexes of the type MABCD may exist in three
[Co(CN)6]3+. isomeric forms.
76. (a) The octahedral coordination compounds of the type A B A C
MA3B3 exhibit fac-mer isomerism.
77. (b) Since Cr3+ in the complex has unpaired electrons in the
d orbital, hence it will absorb visible light and will be
M M
coloured
Ti = [Ar]3d 2 4 s2 ; Ti4 + = 3d 0
5
Cr = [Ar] 3d 4s ; 1 Cr3+ = 3d 3
Zn= [Ar] 3d 4s ; Zn2+= 3d 10
10 2 D C D B
(I) (II)
Sc = [Ar] 3d 1 4s2; Sc3+ = 3d 0
2 A C A C
78. (a) Ni(CN)4 : Number of unpaired electrons = 0
3
Cr(NH3 ) 6 : Number of unpaired electrons = 3
2 M M
Fe(H 2 O) 6 : Number of unpaired electrons = 4
2
Ni(H 2 O)6 : Number of unpaired electrons = 2
D B B D
(III)
79. (d) In Ni NH3 2 Cl 2 , Ni 2 is in sp3 hybridisation,
thus tetrahedral in shape. Hence the four ligands are Similarly, [Pt (py) (NH3) BrCl] may exist in three isomeric
not different to exhibit optical isomerism. In tetrahedral form in which
geometry all the positions are adjacent to one another M = Pt, A = Py, B = NH3, C = Br, D = Cl.
geometrical isomerism is not possible.
80. (b) Ni++ = 3d 8 4s0 83. (b)
(a) [Ti(NH3)6]3+ : 3d1 configuration and thus has one
unpaired electron.
(b) [Cr(NH3)6]3+ : In this complex Cr is in +3 oxidation
Since, the coordination number of Ni in this complex is state.
4, the configuration of Ni++ at first sight shows that the Cr3+ : 3d 3 4s0
complex is paramagnetic with two unpaired electron.
However, experiments show that the complex is
diamagnetic. This is possible when the 3d electrons It has 3 unpaired electrons thus complex is paramagnetic
rearrange against the Hund’s rule as shown below. This NH3 NH3 NH3 NH 3 NH3 NH3
is in accordance with the fact that the ligand involved
here is strong i.e., CN– ion.
Ni++ (after rearrangement) (c) [Co(NH3)6]3+ : In this complex cobalt ion is in + 3
4s 4p oxidation state with 3d 6 configuration.
Co3+,[Ar]3d 6
4s 4p

Hence, now dsp2 hybridization involving one 3d, one [Co(NH3)6]3+

4s and two 4p orbitals, takes place leading to four dsp2
hybrid orbitals, each of which accepts four electron
pairs from CN– ion forming [Ni (CN)4]2– ion. NH3 NH3 NH3 NH3 NH3 NH3
[Ni (CN)4]2–
(inner orbital or d 2sp3 hybrid orbital, low spin complex)
diamagnetic
×× ×× ×× ×× ××
(d) In this complex Zn exists as
Zn++ ion
four dsp2 hybrid bonds Zn++ ion : 3d 10 4s0
Thus, the complex is diamagnetic as it has no unpaired
electron.
 ALTITUDE CLASSES
CHEMISTRY
Zn++ ion in [Zn(NH3)4]2+ 90. (b) Option (b) shows optical isomerism [Co(en)3]3+
NH 3 NH 3 NH 3 NH 3
en 3+ en 3+

Due to presence of paired electrons complex is en Co Co en

diamagnetic in nature.
84. (c) Nickel ions are frequently detected by the formation of
en
red precipitate of the complex of nickel en
dimethylglyoxime, when heated with dimethylglyoxime. d–form Mirror –form
CH3 C NOH ++ Complexes of Zn++ cannot show optical isomerism as
+ Ni
CH3 C NOH they are tetrahedral complexes with plane of symmetry.
3
Co(H2 O)4 (en) have two planes of symmetry
Dimethylglyoxime
hence it is also optically inactive.
OH O [Zn(en)2]2+ cannot show optical isomerism

CH3 C N N C CH3 en 3+
91. (b)
Ni NH3
CH3 C N N C CH3

O OH Co

Nickel dimethylglyoxime NH3

6 2, 2, 2 0,0 en
85. (b) d – t2g eg (in low spin)
cis
12 3+
C.F.S.E = – 0.4 × 6 0 + 3P = + 3P NH 3
5 0
86. (a) Complexes with dsp2 hybridisation are square planar.
So, [PtCl4]2– is square planar in shape.
87. (d) In the given complex we have two bidentate ligands en Co en
(i.e en and C2O4), so coordination number of E is 6
(2 × 2 + 1 × 2 = 6)
Let the oxidation state of E in complex be x, then
[x + (–2) = 1] or x – 2 = 1
NH 3
or x = + 3, so its oxidation state is + 3
Thus option (d) is correct. trans-
88. (a) The SCN– ion can coordinate through S or N atom 92. (c) [Cr (NH3)6]Cl3 is an inner orbital complex, because in
giving rise to linkage isomerism this complex inner d-orbital is used for hybridisation
M SCN thiocyanato (d2 sp3 )
M NCS isothiocyanato. 93. (a) Ligands can be arranged in a series in the orders of
89. (a) CoCl3 .6NH3 x Cl increasing field strength as given below :
2.675g Weak field ligands :

x Cl AgNO3 x AgCl I Br S2 SCN Cl N3 , F

4.78g < Urea, OH– < oxalate
Number of moles of the complex Strong field ligands
2.675 O H 2O NCS EDTA Py, NH3 <
= = 0.01 moles
267.5
Number of moles of AgCl obtained en = SO 3 – < bipy, Phen NO2 CH3
4.78 C6 H 5 CN CO
= 0.03 moles
143.5 Such a series is termed as spectrochemical series. It is
No. of moles of AgCl obtained an experimentally determined series based on the
= 3 × No. of moles of complex absorption of light by complexes with different ligands.
0.03 94. (b) [Cr(en)2Br2]Br
n= 3 dibromidobis (ethylenediamine) chromium (III) bromide.
0.01
3Cl– ions are precipitable 95. (d) [Co(H2O)4(NH3)2]Cl3
Hence the formula of the complex is [Co(NH3)6]Cl3 = Diamminetetraaquacobalt (III) chloride.
 ALTITUDE CLASSES
COORDINATION COMPOUNDS
EXERCISE - 2 7. (a) The given compound may have linkage isomerism due
to presence of NO2 group which may be in the form
1. (b) The crystal field splitting in tetrahedral complexes is lower
–NO2 or –ONO.
4 It may have ionisation isomerism due to presence of
than that in octahedral complexes, and t 0.
9 two ionisable group –NO 2 & –Cl. It may have
2. (b) It is optically active. geometrical isomerism in the form of cis-trans form as
3. (a) Octahedral complexes of the type [MA3 B 3 ] like follows :
[Co(NH3)3Cl3] exhibit fac-mer isomerism. [Co(NH3)4Cl(NO2)]NO2 & [Co(NH3) (NO2)2]Cl
––– ionisation isomers.
Cl Cl
[Co(NH3)5(NO2)2]Cl & [Co(NH3)5(ONO)2]Cl
H3N H3N
––– Linkage isomers
Cl NH3
NO2 NO2
Co Co
H3N NH3 H3N NO2
H3N Cl Cl NH3
Co Co
NH3 Cl NH3 NH3 NH3 NH3
fac-isomer mer-isomer
NO2 NH3
4. (c) As it forms two moles of silver chloride thus it has two Trans-form cis-form
moles of ionisable Cl. Geometrical isomers
[Co ( NH 3 ) 5 NO 2 ]Cl 2 [Co ( NH 3 ) 5 NO 2 ] 2Cl 8. (c) K4[Fe(CN)6] produces maximum number of ions (5) in the
solution.
2Cl 2AgNO3 2AgCl 2NO 3
K4[Fe(CN)6] 4K+ + [Fe(CN)6] –4
5. (d) Optical isomerism is generally shown by octahedral complexes
9. (d) Co (NH3)5 Cl3 [Co(NH3)5Cl]+2 + 2Cl-
of the formula, [Ma 2 b2 c2] n±, [Mabcdef] th [M(AA) 3] n± ,
[M(AA) 2 a 2 ] n± , [M(AA) 2ab] n± and [M(AB) 3 ] th . Thus, Structure is [Co (NH3)5 Cl] Cl2.
among the given compounds, only [Cr(en)3]3+ exhibits optical Now [Co(NH3 )5 Cl]Cl2 2AgNO3
isomerism and exists as a pair of enantiomers.
[Co(NH3 )5 Cl](NO3 )2 2AgCl
en 3+ en 3+ 10. (c) Number of donor atoms (N) in N(CH2CH2NH2)3 are four.
So, N(CH2CH2NH2)3 is a tetradentate ligand.
Cr en en Cr
11. (a) CN– ion acts good complexing as well as reducing
en en
agent.
6. (c) [Co(NH3 )6 ]3+ , Co3+ (27 –3 = 24) 12. (d) Isomers
[Ru(NH3 )4 Cl2 ] ,[Co(NH3 )5 Cl]2 ,
cis and trans none
2
d sp3 (inner octahedral 2
[ Ir ( PR 3 ) 2 H ( CO )] , [ Co ( en ) 2 Cl 2 ]
complex & diamagnetic) cis and trans cis and trans and
[Cr(NH3 )6]3+ , Cr 3+ (24 –3 = 21) optical isomers
13. (d) [Co(NH 3)6][Cr(CN)6] is an ionic compound. Both cation
and anion carry 3 unit charges. It exhibits co-ordination
2 isomerism.
d sp3 (inner octahedral
4–
complex & paramagnetic) 14. (c) [Fe (CN)6]
[Ni(NH3 )6]2+ , Ni2+ (28 – 2 = 26) – no. of unpaired electrons = 0
2–
[MnCl4]
sp3d
2
(outer octahedral – no. of unpaired electrons = 5
complex & paramagnetic) [CoCl4]
2–

[Zn(NH3)6]2+ , Zn 2+ (30 – 2 = 28) – no. of unpaired electrons = 3

The greater the number of unpaired electrons, greater
the magnitude of magnetic moment. Hence the correct
sp3d 2 (outer octahedral order will be
complex &diamagnetic) [MnCl4]– – > [CoCl4]– – > [Fe(CN)6]4–
 ALTITUDE CLASSES
CHEMISTRY
15. (a) Geometrical isomerism is possible only in square planar Where, x electrons in t2g orbital
complexes of the type MA2 B 2 and MA2 BC and for y electrons in eg orbital
octahedral complexes of the type MA4B 2 and MA4BC. CFSE = [0.6 × 1] + [–0.4 × 3] = – 0.6 0
Hence only (ii) will show geometrical isomerism.
16. (d) [Ni X4]2–, the electronic configuration of Ni2+ is 22. (b)

3d 4s 4p
It contains two unpaired electrons and the hybridisation
is sp3 (tetrahedral).
17. (c) (1) [Pt(en) (SCN)2 (NH3)2]0 ; it is not ion trans (green)
(2) [Pt(en) (SCN)2 (NH3 )2 ] 2+ ; it should not be Cl +
platinate HN
3 Cl
(3) [Pt (en) (SCN)2 (NH3)2]2+ : correct name
(4) [Pt(en)2 (SCN) 2 (NH3 )2]2+ ; its coordination Co
number is 8
18. (d) Complex X is [Fe(en)3]2+ ; as 'en' is a strong field ligand
pairing of electrons will take place. HN
3 NH3
NH3
[Fe(en)3]2+ :
cis (violet)
3d 4s 4p
23. (c) Cr2+ d4 4

Mn2+ d5 5
d 2sp3 hybridisation

Hence, hybridisation is d 2sp3 and complex is diamag- Fe2+ d6 4

netic. As it has 3 bidentate symmetrical 'en' ligands so
it will not show geometrical isomerism. Co2+ d7 3
19. (a) [MnO4]2– ; Mn is in +6 oxidation state. Electronic
Minimum paramagnetic behaviour = [Co (H2O)6]2+
configuration is [Ar]18 3d 14s0 . As it contains one 24. (a) As positive charge on the central metal atom increases,
unpaired electron it is paramagnetic and green coloured the less readily the metal can donate electron density
[TiCl6]2–, [VO4]3– and CrO2Cl2 are diamagnetic as all into the * orbitals of CO ligand (donation of electron
electrons are paired. density into * orbitals of CO result in weakening of
20. (d) When excess of AgNO3 and BaCl2 are added to solution X. C – O bond). Hence, the C – O bond would be strongest
in [Mn(CO)6]+.
[Co(NH3 )5 Br]Cl2 2AgNO3 25. (a) [Ni(NH3)6]2+
1mole 2 moles
0.02 mole
Ni2+ = 3d 8, according to CFT = t 62g eg2 therefore,
[Co(NH3 )5 Br](NO3 )2 2AgCl(ppt.)(Y) hybridisation is sp3d 2 and complex is paramagnetic.
1mole 2moles 26. (a) In octahedral complex the magnitude of o will be
0.02 2 0.04 mole
highest in a complex having strongest ligand. Out of
the given ligands CN– is strongest. So, o will be
[Co(NH 3 )5 Cl]SO 4 BaCl 2
highest for [Co(CN)6]3–. Thus option (a) is correct.
1mole
0.02 mole
NH3 NH3
27. (c) NH3
[Co(NH3 )5 Cl]Cl2 BaSO 4 (ppt.) (Z) NH3
1mole
0.02mole
en Co Co en
21. (d) d 4 in high spin octahedral complex
eg —
en en
t 2g
3
Enantiomers of cis- Co(en) 2 (NH 3 ) 2
CFSE = (–0.4x + 0.6y) 0
 ALTITUDE CLASSES
COORDINATION COMPOUNDS
28. (d) An anionic carbonyl complex can delocalise more
3d 4s 4p
electron density to antibonding pi-orbital of CO and
hence, lowers the bond order.
29. (c) The correct IUPAC name of the given compound is
tetramminenickel (II) - tetrachloronickelate (II) thus (c) sp3
is the correct answer.
30. (b) In carbonyls O.S. of metal is zero No. of unpaired electrons = 2
In [Ni(CO)4], the oxidation state of nickel is zero. Its
Magnetic moment, = 2.82 BM.
configuration in Ni(CO)4 is

3d 4s 4p
[Ni(CO)4] ; 35. (c) Complex No. of electrons No. of unpaired
in outer d electron (s)
sp3 hybridisation orbital
In [Ni(CN)4]2– the oxidation state of Ni is 2+ and its [Fe(CN)6]
3–
3d
5 –
1 (CN causes
configuration is pairing of
electrons)
3d 4s 4p 3+ 6 0
[Ni(CN)4]2 [Co(NH3 )6] 3d
[Co(oxal.)3]
3–
3d
6 0
2
dsp hybridisation [Ni(H2 O)6 ]
2+
3d
8 2
2– 8 –
Thus the hybridisations of nickel in these compounds [Pt(CN)4 ] 5d 0 (CN causes
are sp3 and dsp2 respectively. pairing of
electrons)
Hence (b) is the correct answer.
[Zn(H2 O)6]
2+
3d
10 0
31. (a) Chromium in Cr(CO)6 is in zero oxidation state and has
[Ar]18 3d 54s 1 as the electronic configuration. However,
CO is a strong ligand, hence pairing up of electrons
takes place leading to following configuration in Thus L, M, O and P are diamagnetic.
Cr(CO)6. 36. (c) In both states (paramagnetic and diamagnetic) of the
given complex, Ni exists as Ni2+ whose electronic
3d 4s 4p configuration is [Ar] 3d 84s0.
3d 4s 4p
d 2 sp3 Hybridisation Ni2+ :
Since the complex has no unpaired electron, its magnetic sp 3
moment is zero.
32. (b) Ionisation isomer of [Cr(H2 O) 4 Cl(NO 2 )]Cl is In the above paramagnetic state the geometry of the
complex is sp3 giving tetrahedral geometry.
[Cr(H2O)4Cl2]NO2.
33. (c) The correct structure of EDTA is The diamagnetic state is achieved by pairing of
electrons in 3d orbital.
HOOC–H2C CH2–COOH
N – CH2 – CH2 – N 3d 4s 4p
HOOC–H2C CH2–COOH

34. (b) [NiCl4]2–, O.S. of Ni = +2

Ni(28) = 3d 8 4s2 d sp 2

3d Thus the geometry of the complex will be dsp2 giving

4s 4p
square planar geometry.
37. (c) Octahedral coordination entities of the type Ma3b3
exhibit geometrical isomerism. The compound exists
both as facial and meridional isomers, both contain
plane of symmetry
 ALTITUDE CLASSES
CHEMISTRY
41. (c) It is correct statement that NF3 is a weaker ligand than
NH3 NH3 N(CH3 ) 3 , the reason is that fluorine is highly
Cl NH3 NH3 Cl electronegative therefore, it with draw electrons from
nitrogen atom. Hence, the lone pair of nitrogen atom
Co Co
cannot be ligated. While N(CH3)3 is a strong ligand
NH3 Cl Cl because CH3 is electron releasing group.
Cl
Cl NH3 42. (b) Both statement-1 and statement-2 are true but
fac- mer statement-2 is not the correct explanation of statement-
1. [Fe(CN)6 ]3– is weakly paramagnetic as it has
38. (b) 39. (a) 40. (c) unpaired electrons while [Fe(CN)6]2– has no unpaired
electron.
Cu 2AgNO 3 Cu(NO3 ) 2 2Ag
It is diamagnetic.
(M) (N) Blue 43. (a) Both statement-1 and statement-2 are true and
statement-2 is the correct explanation of statement-1.
NaCl AgNO 3 AgCl NaNO3
[Sc(H2O6]3+ has no unpaired electron in its d subshell
(remaining) (O) and thus d–d transition is not possible whereas
2AgCl 2NH3 (aq) Ag(NH3 ) 2 [Ti(H2O)6]3+ has one unpaired electron in its d subshell
which gives rise to d–d transition to impart colour.
Soluble

Cu(NO 3 ) 2 4NH 3 ( aq) [Cu(NH 3 ) 4 ](NO3 ) 2

(remaining) (Deep blue colour)