Complex Coumpounds
Complex Coumpounds
Complex Coumpounds
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COMPLEX COMPOUNDS
Ø Secondary valency (Non-Ionisable valency)
SYNOPSIS
i) It is satisfied by anions or neutral molecules
Co-ordination Compounds or rarely with cations. The groups satisfying
Ø Double Salt : secondary valencies are called ligands.
1) Double salts exist only in solid state and ii) The number of secondary valencies is equal
dissociate into ions in water to coordination number.
2) They lose their identity in solution. iii) It is represented by thick lines while writing
3) The properties of double salt are essentially the structure of the complex.
the same as those of the constituent compounds Ø In some complexes the same groups satisfies
4) In double salts, metal ion exhibit their normal both primary and secondary valencies.
valency. Ø The ligands are directed in space around the
5) Double salts contain ionic bonds central metal atom in different ways. This leads
to a definite geometry to the molecule.
Ex: i) KCl . MgCl2 .6 H 2O (Carnallite)
ii) K 2 SO4 . Al2 ( SO4 )3 .24 H 2O (Potash alum)
iii)FeSO4 . (NH4)2 SO4 . 6H2O (Mohr’s salt)
Ø Coordination compound :
1) They exist in the solid state as well as in
solution.
2) They donot completely lose their identity in
solution.
3) The properties of coordinate compounds are
different from the constituent compounds.
4) In coordination compound, metal ion is
surrounded by a number of anions or neutral
molecules. The metal ion exhibits more than
its normal valency.
5) Coordinate comounds may have ionic as well
as coordinate bonds.
Ex: K4[Fe(CN)6], K3[Fe(CN)6], Na3 Ag ( S 2O3 )2
Ø The transition metal ions form co-ordinate
compounds because
i) They have small size.
ii) They have high nuclear charge
iii) They have vacant d-orbitals
iv) They can accept lone pairs of electrons.
Ø Werner’s Theory: According to Werner
(father of Co-ordination chemistry) transition
metals possess two types of valencies.
a) Primary valency (Ionisable valency)
b) Secondary valency (non ionisable valency)
Ø Primary Valency (Ionisable Valency)
i) It is referred to as oxidation state.
ii) It is satisfied by only anions.
iii) It is represented by dotted lines while writing
the structure of complex.
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Defects in Werner’s Theory Definitions of Some Important Terms
Ø This theory does not relate the electronic in co-ordination Compounds
configuration of metal with the formation of the Oxidation number of central atom: The
complex. oxidation number of the central atom in a
Ø It is known now that the metal tries to acquire complex is defined as the charge it would carry
the nearest inert gas configuration during the if all the ligands are removed along with the
formation of complex electron pairs that are shared with the central
Ø This theory does not explain the reason for the atom. It is also called primary valency.
colour of the complex Ø The oxidation number is represented by a
Ø This theory does not explain the magnetic Roman numerical in parenthesis after the name
behaviour of complexes. of the metal.
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Ø If the same ligand can donate lone pairs from Ø Point of Attachment: When a ligand can
more than one centre, they are named as coordinate through more than one atom, then
bidentate, tridentate etc, depending on the the point of attachment of the ligand is indicated
number of lone pairs donated. by putting the symbol of the atom through which
Ex: NH 2CH 2CH 2 NH 2 . coordination occurs, after the name of the ligand.
Ø The number of bidentate, tridentate etc ligands Sometimes, different names are used for
is mentioned with bis, tris, tetrakis, etc. If they alternative modes of attachment.
already contain di, tri, tetra etc. in their names. Ex: NO2− can co-ordinate through -N (or) -O.
Ex: Pt Br2 ( NH 2 CH 2 CH 2 NH 2 )2 Cl2 is If it co-ordinates through N, it is called nitrito
-N (or simply as nitro). On the other hand, if
named as dibromobis (1, 2-ethane diamine) it co-ordinates through -O, (-ONO-), it is called
Platinum(IV) chloride. nitrito-O.
Ø Ending Names: When the complex is anionic,
the name of the central metal atom ends with - − NO2− (through N) −O NO − (through -O)
ate. For cationic and neutral complexes the Nitrito -N (or) Nitrito-O (or)
name of the metal is written without any Simply nitro Simply nitrito
characteristic ending. − SCN − (through -S) − NCS − - (through -N)
Ex: Cationic complex : thio cyanato (or) isothio cyanato (or)
Co ( NH 3 )6 Cl3 -Hexamminecobalt(III) thio cyanato-S thio cyanato-N
chloride Cationic Complexes
Ex :Neutral complex : Ø Co ( NH 3 )6 Cl3
Ni (CO )4 - Tetracarbonylnickel(0) Hexamminecobalt (III) chloride
Ex :Anionic complex :
Ø Pt (Cl )( NH ) Cl
K Pt Cl5 ( NH 3 ) - 3 5
3
Pentaamminechloroplatinum (IV) chloride
Potassium amminepentachloroplatinate(IV)
Ø If the complex is anion, the name of the metal Ø CrCl ( NO2 )( NH 3 )4 NO3
should be taken from latin language. Tetraamminechloronitrochromium(III) nitrate
Ex : Cu - Cuprum – Cuprate
Ø Pt ( NH 3 )6 Cl4
Sn - Stannum – Stannate
Fe - Ferrum – Ferrate Hexammineplatinum(IV) chloride.
Pb - Plumbum – Plumbate Co ( NH 3 ) ( H 2O ) Cl Cl2
Ø 4
Ag - Argentum – Argentate
Au - Aurum – Aurate Tetraammineaquachlorocobalt(III) chloride.
Cr - Chromium – Chromate +
Ø Cr ( H 2O )4 Cl2
Ni - Nickel – Nickelate
Tetraaquodichlorochromium(III)ion.
Oxidation State of Central Metal ion:
The oxidation state of the central metal ion is Ø Ag ( NH 3 )2 Cl Diamminesilver(I) chloride.
designated by a Roman numerical (such as II,
III, IV) in the brackets at the end of the name of Ø Ti ( H 2O )6 Cl3
the metal of the complex. Hexaaquotitanium(III) chloride.
Ex : CoCl ( NH 3 )5 Cl2 - Ø Cr ( NH 3 )6 Cl3
Pentaamminechlorocobalt(III) chloride. Hexaamminechromium(III) chloride.
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Ø Cu (en )2 SO4 Neutral Complex
Ø Co ( NH 3 )3 Cl3
Bis(ethylenediamine)copper(II) sulphate.
Ø Cu ( NH 3 )4 SO4 Triamminetrichlorocobalt(III)
Ø Pt ( NH 3 ) Br2Cl2
Tetraamminecopper(II) sulphate 2
Diamminedibromodichloroplatinum(IV)
Ø Fe ( H 2O )4 (C2O4 ) SO4
2
Ø Cr ( H 2O )3 Cl3 .3H 2O
Tetraaquaoxalatoiron(III) sulphate.
Triaquotrichlorochromium(III)trihydrate.
Ø Fe ( H 2O ) NO + SO4
5 Ø Fe (CO )5 Pentacarbonyliron(O)
Pentaaquanitrasonium(I) sulphate
Ø Co ( NH 3 )3 ( NO2 )3
Anionic Complexes
Triamminetrinitrocobalt (III)
Ø K 4 Fe (CN )6
Isomerism in Complexes: Substances
Potassium hexacyanoferrate(II) having the same molecular formula but have
Ø Na2 [Zn Cl4 ] Sodium tetrachlorozincate(II) different structures (or) properties are known as
isomers. The phenomenon of the existence of
Ø K 3 Fe (CN )5 NO isomers is known as isomerism. It is two types
1) Structural isomerism 2) Stereo isomerism
Potassium pentacyanonitrosylferrate(II)
Ø Structural Isomerism: This isomerism arises
Ø K 3 Fe (CN )6 due to the difference in the structures of
complexes.
Potassium hexacyanoferrate(III)
Ø Ionisation Isomerism: Complexes which
Ø K 3 Cr (C2O4 )3 have the same molecular formula but gives
different ions in solution are called Ionisation
Potassium trioxalatochromate(III)
isomers and the phenomenon is called ionisation
Ø K 3 CoCl2 (C2O4 )2 isomerism.
Potassium dichlorodioxalatocobaltate(III) Ex: Co ( NH 3 )5 SO4 Br and Co ( NH 3 )5 Br SO4
Ø K2 [ HgI4 ] Potassium tetraIodomercurate(II). Ø Ionisation isomers are formed by the interchange
of the position of ligands inside (or) out side
Ø K 2 [ Pt Cl6 ] the coordination sphere.
Potassium hexachloroplatinate(IV) Ø Ionisation isomerism arises, when the counter
Ø Na Ag (CN )2 ions in a complex compound can also function
as ligands.
Sodium dicyanoargentate(I) Ø In the ionic complex compounds, the ion having
−2 an opposite charge to that of the complex ion is
Ø Ni (CN )4 called counter ion.
Tetracyanonickelate(II) ion. i) K +in K 4 Fe (CN )6
Ø K 3 Cr (CN )6
ii) Cl −ions in Co ( NH 3 )6 Cl3
Potassium hexacyanochromate(III)
Ø The following pairs of compounds give different
Ø K 3 Co (CN )6 ions in solutions.
Potassium hexacyanocobaltate(III) Ø Co ( NO3 )( NH 3 )5 SO4 gives sulphate ions
Ø Na3 Ag ( S2O3 )2 while Co ( SO4 )( NH 3 )5 ( NO3 ) gives nitrate
Sodium bis(thio sulphato)argentate(I) ions.
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Ø Linkage Isomerism: Complex with
Ø Co ( NO3 )( NH 3 )5 SO4 gives white
ambidentate ligands shows this type of
precipitate with BaCl2 solution. isomerism. A mono dentate ligand with two (or)
more donar atoms is called ambidentate ligand.
Ø Co ( SO4 )( NH 3 )5 ( NO3 ) cannot give white
+2
Ex: [Co( NO2 )( NH 3 )5 ] &
+2
[Co(ONO)( NH 3 )5 ]
precipitate with BaCl2 solution.
Ø Co-ordination Isomerism: It arises due to
Ø Pt Cl2 ( NH 3 )4 Br2 gives Br − ions. So it the mutual exchange of ligands between anionic
and cationic spheres.
can give light yellow precipitate with aqueous
AgNO3 solution. Ex: [Co( NH 3 )6 ][Cr (CN )6 ] &
molecules in and outside the coordination Ø Stereo Isomerism: Isomers which have the
sphere. same position of atoms (or) groups but differ in
Ø This type of isomers differ in number of water the spatial arrangements around the central atom
molecules as ligands and as hydrated molecules. are called stereo isomers and the phenomenon
Ex : CrCl3 .6 H 2O molecular formula has four is called stereo isomerism. It is classified into
possible isomers. They are two types.
(a) Geometrical isomerism
Cr ( H 2O )6 Cl3 - violet coloured;
(b) optical isomerism.
Cr ( H 2O )5 Cl Cl2 .H 2O - light green Geometrical Isomerism: Geometrical
isomerism is due to ligands occupying different
coloured
positions around the central metal atom (or) ion.
CrCl2 ( H 2O )4 Cl.2 H 2O - dark green Ø When two identical ligands occupy adjacent
coloured positions, the isomer is called cis-isomer.
Ø When two identical ligands occupy opposite
CrCl3 ( H 2O )3 .3H 2O - brown coloured
positions, the isomer is called trans-isomer.
Ø Geometrical isomerism is very much common
Ø In the same manner CoCl3 ( H 2O )6 complex
in coordination number 4 and 6 complexes.
has the isomers Ø Tetrahedral complexes cannot exhibit
CoCl ( H 2O )5 Cl2 .H 2O ; geometrical isomerism.
Ø Square planar complexes of the type
CoCl2 ( H 2O )4 Cl.2 H 2O
Ma4 , Ma3b, Mab3 do not exhibit geometrical
and CoCl3 ( H 2O )3 .3H 2O . isomerism.
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Ø Square planar complexes of the type
Ma2b2 , Ma2bc and Mabcd exhibit
geometrical isomerism.
Ex : Pt ( NH 3 )2 Cl2
Ø Octahedral complexes
Cis Positions : 1,2; 2,3; 3,4; 1.4 Cis Positions : 1,2; 1,3; 1,4; 1,5; 2,3; 2,5;
Trans Positions : 1,3; 2,4 3,4; 4,5; 2,6; 3,6; 4,6; 5,6
Trans Positions: 1,6; 2,4; 3,5
Ø Mabcd type of complexes will have 3
geometrical isomers i.e. 2cis and 1 trans isomer Ø octahedral complexes of the type Ma6 , Ma5b ,
Ø Square planer complex having unsymmetrical Mab5 do not exhibit geometrical isomerism.
bidentate chelating ligands with general Ø Octahedral complexes of the type
±n
formula M ( AB )2 exhibit geometrical Ma4b2 , Ma4bc and Ma3b3 complexes exhibit
isomerism geometrical isomerism.
+
Ex : CoCl2 ( NH 3 )4
Ex:
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Type of Geometry of Examples
hybridization complex
+
sp Linear or Ag ( NH 3 )2 ,
( 4s 4 p )
+
diagonal Ag (CN )2
CN = 2
[ HgI 3 ]
−
sp 2 Trigonal planar
Ø Octahedral complexes containing (4s 4 p ) 2
optical isomerism.
(4s 4 p ) 3
Zn ( NH 3 )4
2+
±n
Cis − M ( AA ) a2b2 , and X = Cl − , Br − , I −
2−
Cis − M ( AA )( BB ) a2
±n
are optically active. dsp 2 Square planar Ni (CN )4
compound is CN = 5
CN = 5
3+
VBT of Co-ordination Compounds: d 2 sp 3 Inner orbital Cr ( NH 3 )6
Ø The central metal atom or ion makes available
a number of empty s, p and d atomic orbitals (3d x2 − y 2 )
3d z 2 4s 4 p 3 octahedral Mn (CN )6
3−
3−
equal to its coordination number. These vacant CN = 6 Fe (CN )6 etc
orbitals hybridise together to form hybrid
[ FeF6 ]
3−
orbitals. These hybrid orbitals are vacant, sp 3 d 2 Outer orbital
equivalent in energy and have definite geometry.
The most common hybridizations in complex ( 4 s 4 p 4d 3
x2 − y 2 )
4d z 2 octahedral Co ( H 2O )6
2+
are given. 2+
CN = 6 Ni ( NH 3 )6
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Ø Each ligands have atleast one sigma orbital Examples of Complexes
containing alone pair of electrons. 4−
6.
3+
Complex/ion : Co ( NH 3 )6 Co 3+ 10. Complex/ion : Ni (CN )4 Ni 2+
Electronic configuration and hybridisation:
Electronic configuration and hybridisation:
Geometry : Tetrahedral
Geometry : Octahedral No.of unpaired electrons/paramagnetic
No. of unpaired electrons/paramagnetic character:
character: 4-Paramagnetic. µ = 4.85BM 2-Paramagnetic
µ = 2.8BM
Complex/ion: [CuCl4 ] Cu 2 +
2−
8.
12. Complex/ion : Ni (CO )4 Ni 0
Electronic configuration and hybridisation:
Electronic configuration and hybridisation:
Geometry : Tetrahedral
Geometry : Tetrahedral
No. of unpaired electrons/paramagnetic
No. of unpaired electrons/paramagnetic
character:1-Paramagnetic. µ = 1.75BM character: 0-Diamagnetic
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2−
13. Complex/ion : Pt (CN )4 Pt 2+ Hence hybridisation is dsp 2 (square planar). But
Electronic configuration and hybridisation: Cl is weak field ligand. So, rearrangement of
d-electrons is not possible. Hence the
configuration of Ni +2 is
( sp ) .
3
Br is weak field ligand so,
EAN of Co = 27 − 3 + 2 × 6 = 36
rearrangement of d-electrons is not possible. 3)In Ni (CO )4 complex
Hence complex is tetrahedral ( sp3 - EAN of Ni = 28 − 0 + 2 × 4 = 36
hybridization). 2−
4)In Ni (CN )4 complex ion
2−
W.E-4: Ni (CN )4 is inner complex but
EAN of Ni = 28 − 2 + 2 × 4 = 34
[ NiCl4 ]
2−
is outer complex. Give the reason. 3−
5)In Fe (CN )6 complex ion
−2
Sol. CN − is strong field ligand. So. in Ni (CN )4 EAN of Fe = 26 − 3 + 2 × 6 = 35
6)In K 2 [ Pt Cl6 ] complex
ion Ni +2 configuration is
EAN of Pt = 78 − 4 + 2 × 6 = 86 [ Rn ]
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Ø In some complexes, the EAN is not equal to the Ø In a free metal atom, all five orbitals of d-sub
atomic number of the nearest inert gas. Yet they shell have same energy. They are called
are stable. degenerated orbitals.
2− When ligands approach the central metal atoms,
Ex: K 3 Fe (CN )6 , Ni (CN )4 . the electrons of d-orbitals of metal suffer
repulsions by lp of ligands as a result digeneracy
W.E-5: If [ AuCl6 ]
y−
follows EAN rule, then the
is broken and d-orbitals are split into two sets
oxidation state of Au is (At. no. of Au =79 of orbitals.
and At. no. of Rn =86). Ø a) Three of d-orbitals i.e., d xy , d yz and d zx which
Sol. EAN = Z - x + n x y are oriented in between the co-ordinate axes are
86 = 79 - x + 6 x 2 ; x = +5
called t2 g -orbitals.
W.E-6: If Ni (CO )x follows EAN rule, then x - Ø b) The other two d-orbitals i.e., d x2 − y 2 and d z 2
value is which are oriented along the axes are called
Sol. EAN = Z - x + n x y
eg -orbitals.
36 = 28 - 0 + n x 2 ; n = 4.
Ø This spliting of d-orbitals of metal ion under
Formula of compound is Ni (CO )4 . the influence of approaching ligands is called
crystal field spliting. It is designated by ∆ and
Crystal Field Theory (CFT) is called crystal field splitting energy.
Ø This theory is based on theoretical work of Bethe Ø The decreasing order of field strength among
& Van Vleck on interaction of ionic crystals. some of the ligands are
Ø Ligands are either anion or neutral molecule Weak field ligand
containing atleast one lone pair of electron. The
anions are regarded as negative point charges. I − < Br − < SCN − < Cl − < S 2− < NO3−
The neutral ligands are regarded as point dipoles. < F − < OH − < ox 2− < O 2− < H 2O
Ø The neutral ligands are polarised by positive
charges of metal ion. Strong Field ligands
NCS − < Edta 4− < py ≈ NH 3 < en
< dipy < o − phen < NO2 − < CN − < CO
Ø Central metal ion is surrounded by anions or
neutral ligands. For d 4 ions, two possible patterns of electron
distribution.
1) If ∆ 0 < p, the fourth electron enters one of
3 1
the eg orbital giving the configuration t2g eg .
Ligands for which ∆ 0 < p are known as weak
field ligands and form high spin complexes.
2) If ∆ 0 > p , it becomes more energetically
favourable for fourth electron to occupy a t2 g
Ø The electrostatic attraction between nucleus of 4 0
orbital with configuration t2g eg . Ligands which
cation and negative charge of ligands.
Ø Repulsive forces arise between lp of ligands, produce this effect are known as strong field
ligands and form low spin complex.
electrons of d-orbitals of central metal atom.
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Crystal Field Splitting in octahedral In this situation, the t2 g set of orbital lie
and tetrahedral complexes relatively nearer to the approaching ligands and
Ø In octahedral complexes, the six ligands therefore t2 g set of d-orbitals have higher energy
approach the central metal ion along the co-
than eg set of orbitals.
ordinate axes i.e., the axes of d x2 − y 2 and d z 2
Ø Relationship between ∆ t and ∆ 0 is given as ;
orbitals. Consequently, the eg set of orbitals has
higher energy than t2 g orbitals. 4
∆t = ∆o
9
Ø In tetrahedral complex, four ligands may be
imagined to occupy the alternate corners of the Ø While entering electrons into d-orbitals after
cube and the metal ion at the centre of the cube. splitting in ligand field, Hunds and pauli’s
principle to be followed.
Ø
Nature of the metal ion:
For the analogous entities within a group, ∆
(d x2 − y 2 )
or d z 2 orbital by absorbing light equal
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Ø For example, three complexes of Co 3+ as 2+ 2+
Ni ( H2O)4 en (aq) + en(aq) → Ni ( H2O)2 (en)2 (aq) + 2H2O
[Co(H2O)6]3+ ,[Co(NH3)6]3+ and [Co(CN)6]3-.
According to spectrochemical series, the crystal blue / purple
field splitting energies will be in the order of 2+ 2+
−
Ni ( H2O)2 (en)2 (aq) + en(aq) →Ni (en)3 (aq) + 2H2O
ligands as H 2O < NH 3 < CN
Violet
These colour changes are observed due to the
presence of different ligands in the complexes.
Rules for Writing the Formulae of
Co-ordination Compounds
Ø All mononuclear complex entities contain a
single central metal atom, which is symbolised
first.
Ø If more than one ligand of each type is present,
they represented in the following order.
negative, neutral, positive
Ex:-
+2
Correct formula : FeCl (CO )3 NO + .
Ø Complete co-ordination entity is enclosed in
square brackets. Different species present in the
formula are written continuously without
leaving space.
Ø Charge of anionic or cationic complex is
indicated outside the square brackets as a right
superscript.
3+
W.E-9:In Ti ( H 2O )6 complex Ti +3 has only
Ø It may be noted that in the absence of ligands,
the crystal field splitting does not occur and one electron in 3d-orbital. Its spectrum shows
hence the substance is colourless. For example, a single absorption peak of 5000 A0 then
removal of water from [Ti(H2O)6]Cl3, on heating corresponding energy is
makes it colourless. Similarly, anhydrous CuSO4
N 0 .hc
is white but CuSO4.5H2O is blue in colour. Sol. E =
Ø The effect of the ligand on the colour of a λ
complex may be illustrated by taking the
6.023 × 1023 × 6.63 × 10−34 × 3 × 108
example of [Ni(H2O)6]2+. This is formed when =
nickel chloride dissolved in water. The aqueous 5 × 10−7
solution of the complex has green colour. If the = 239 kJ / mol
bidentate ligand, ethane-1,2-diamine (en) is
progressively added in the molar ratio of en : Ni Metal Carbonyls
as 1 : 1, 2 : 1 and 3 : 1, the following series of Ø Class of coordination compound known as metal
reactions occur resulting different colour carbonyls in which carbon monoxide (CO) acts
changes as : as ligand.
2+ 2+
N i ( H 2 O )6 ( a q ) + en ( a q ) → N i ( H 2 O )4 en + 2 H 2 O Ø These are also called homoleptic carbonyls
P a le b lu e
(compounds containing carbonyl ligands only).
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Ø These compounds contain both (ii) There is a π -overlap involving donation of
σ and π character. electrons from filled metal d-orbitals into vacant
Structure of metal carbonyls anti-bonding π * molecular orbitals of CO. This
Ø Tetracarbonyl nickel (0) is tetrahedral. results into the formation of M → C π bond.
Ø Pentacarbonyl iron (0) is trigonal bipyramidal. This is also called back donation or back
Ø Hexacarbonyl chromium (0) is octahedral. bonding.The metal to ligand bonding creates a
Ø Some carbonyls have metal-metal bonds. synergic effect which strengthens the bond
Ø Decacarbonyl dimanganese (0) is made up of between CO and the metal.
two square pyramidal Mn(CO)5 units joined
by Mn-Mn bond. Stability of Coordination
Ø Octacarbonyl dicobalt (0) has a Co-Co bond Ø Compounds in Solution: The stability of a
bridged by two CO-CO groups. complex in solution refers to the degree of
association between the two species involved
in the state of equilibrium.
Ø The magnitude of the (stability or formation)
equilibrium constant for the association,
quantitatively expresses the stability.
Ø we have a reaction of the type:
M + 4 L P ML4 then the larger the stability
constant, the higher the proportion of ML4 that
exists in solution. Free metal ions rarely exist
in the solution so that M will usually be
surrounded by solvent molecules which will
compete with the ligand molecules, L, and be
successively replaced by them. we generally
ignore these solvent molecules and write four
stability constants as follows:
M + L P ML K1=[ML]/[M][L]
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+2
W.E-10: Zn +2 + 2 NH 3 S Zn ( NH 3 )2 ; K1 = 2 ×10−3 K 4 Fe (CN )6 → 4 K + + Fe (CN )6
4−
+2
Zn ( NH 3 )2 + 2 NH 3 S K 2 = 1.5 × 10−3 ?
Find out the instability constant ? Ex : Fe 2+ + 6CN −
Sol. K C = K1.K 2 = 2 × 10 −3 × 1.5 × 10−3 = 3 × 10 −6 ( feebly dissociated )
Instability constant is inverse of stability
Imperfect or normal complexes: These are
constant
the compounds in which complex ion is less
1 1 stable and is reversibly dissociated to give
= −6
= 3.3 × 105
K C 3 × 10 enough simple ions.
2−
Application of Complexes: CuSO4 K 2 Cd (CN )4 → 2 K + + Cd (CN )4
solution, when mixed with aqueous ammonia, ?
2+
gives a deep blue complex soluble in water. This Ex : Cd + 4CN −
is used in the identification of Cu +2 ion. It is ( appreciably dissociated )
due to the formation of the complex
+2
Based on reactivity complex are two types
Cu ( NH 3 )4 Ø Labile complexes : Those complexes are
Ø Ammonium salts are identified by Nessler’s highly reactive, i.e., in which ligands can be
readily replaced by other ligands are called labile
reagent. It is a complex K 2 [ HgI 4 ] -a colourless complexes.
solution. Ø Inert complexes : Those complexes are less
Ø Fe(III) ion in group III is identified as reactive, i.e., in which the ligands cannot be
[Fe(NCS)6]3- ion which has blood red colour. readily replaced by other ligands are called inert
Ø In Photography the developing of negative is complexes.
based on complex formation.
C.U.Q
AgBr + 2 Na2 S 2O3 → Na3 Ag ( S 2O3 )2 + NaBr
WERNER’S THEORY
Ø The extraction of silver, gold from their ores
1. The following does not give a precipitate
makes use of a complex compound formed by
either with AgNO3 or BaCl2
leaching their ores with NaCN solution.
1) [Co (NH3)5 Cl] SO4 2) [Co (NH3)3 Cl3]
Ø In the electroplating of Ag, large amounts of
silver are held as the complex, K[Ag(CN)2]. 3) [Co (NH3)4 Cl2]Cl 4) [Co(NH 3 )2 Cl4 ]Cl
Ø Haemoglobin is a complex which contains Fe+2 2. Which of the following has highest molar
ions. conductivity?
Ø Chlorophyll is a complex which contains Mg+2 1) [Co (NH3)6] Cl3 2) [Co (NH3)5Cl] Cl2
ions. 3) [Co (NH3)4 Cl2] Cl 4) [Co (NH3)3 Cl3]
Ø Vitamin - B12 is a complex which contains Co3+ 3. Transition elements form complexes readily
ions. because
ADDITIONAL TOPICS i) Small size of cation ii) Large ionic Charge
iii) Vacant d orbitals
Ø Based on stability complexes are two types
The correct statements is / are:
Perfect or penetrating complexes These are
1) i only 2) ii only 3) i & ii 4) i,ii,iii
the compounds in which complex ion is fairly
stable and is either not dissociated or feebly 4. The ionizable valency of Ni in Ni(CO)4 is
dissociated in solution. e.g., 1) 2 2) 4 3) 0 4) 1
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5. According to Werner’s theory transition 16. Which of the following is cationic complex
metals possesses
1) K 4 Fe (CN )6 2) Ni (CO )4
1) only one type of valency
2) two types of valencies 3) Co ( NH 3 )3 Cl3 4) Cu ( NH 3 )4 SO 4
3) three types of valencies 17. The no. of moles of AgCl obtained when
4) four types of valencies excess AgNO 3 is added to one mole of
6. The primary valency of the metal ion is [Cr(NH3)4Cl2]Cl
satisfied by 1) 1 2) 2 3) 3 4) 4
1) neutral molecules 2) positive ions 18. Ligand in a metal carbonyl complex is
3) negative ions 4) all the above 1) NH3 2) CO 3) CN- 4) SCN-
7. No of ionizable & non-ionizable Cl− ions in 19. The no. of moles of AgCl precipitated when
excess of AgNO3 is mixed with one mole of
CoCl3 5 NH 3 representively are [Cr(NH3)3 Cl3] is
1) 3, 0 2) 2, 1 3) 1, 2 4) 0, 3 1) 0 2) 1 3) 2 4) 3
8. Central metal ion in complex compound acts NOMENCLATURE
as
1) Lewis acid 2) Lewis base 20. IUPAC name of the complex CoCl3 5 NH 3 is
3) Arrhenius acid 4) Arrhenius base 1) Cobalt trichloride penta amonium
9. Which one of the following acts as a Lewis 2) Penta amine carbonyl chloride
base in complexes 3) Trichloro penta amino cobalt
1) CO2 2) BF3 3) NH3 4) BCl3 4) Pentaaminechlorocobalt ( III ) chloride
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26. The effective atomic number of central metal CFT
ion is wrongly calculated in the following 35. Which of the following system has maximum
complex? number of the unpaired electrons in an inner
1. In Ni (CO )4 the EAN of Ni is 36
octahedral complex ?
1) d 4 2) d 9 3) d 7 4) d 5
2. In K 2 Ni (CN )4 the EAN of Ni is 36 36. In an octahedral crystal field, the correct set
of low energy orbitals are
3. In K 3 Fe (CN )6 the EAN of Fe 35 1) d xy , d xz , d x2 − y 2 2) d x2 − y 2 , d z 2
2. Co ( NH 3 )6 Cl3 gives more number ions. d 9 − t26g eg3 , so one unpaired electron
7. 2, 1 d 7 − t26g e1g , so one unpaired electron
8. In any complex central metal ion acts as Lewis
acid {electron pair acceptor) and Ligands acts d 5 − t25g eg0 , so one unpaired electron
as Lewis base {electron pair donar)
4
9. NH 3 acts as ligand. 37. ∆ t = ∆0
9
12. In metal carbonyl compounds the oxidation
number of metal is zero because CO is neutral. 40. Formula of Nessler’s reagent is K 2 HgI 4 .
−3 41. As increase of electron density back bonding
13. K 3 Fe (CN )6 → 3K + + Fe (CN )6 tendence of π bond increases, so C-O bond
= 4 moles order decreases.
ISOMERISM 3) V (C O )6 4) Cr (CO )6
9. Which of the following does not exhibit 16. The number of ions formed when
optical isomer ? cupraammonium sulphate is dissolved in
1) Co ( NH 3 )3 Cl3 2) Co (en )3 Cl3 water
1) 1 2) 2 3) 4 4) zero
3) Co (en )2 Cl2 Cl 4) Co (en )( NH 3 )2 Cl2 Cl
CFT
10. Co-ordination compounds Pt ( NH 3 )3 ( NCS ) 17. Which of the following is correct
arrangement of ligands in terms of field
and Pt ( NH 3 )3 ( SCN ) are example of -- strength
isomerism
1) Cl − < F − < NCS − < NH 3 < CN −
1) Co-ordination 2) Ionization
3) Linkage 4) Optical 2) NH 3 < F − < Cl − < NCS − < CN −
11. Geometrical isomerism is observed in
1) Tetrahedral complex 3) Cl − < F − < NCS − < CN − < NH 3
2) Square planar complex 4) NH 3 < CN − < NCS − < Cl − < F −
3) Tined complexes 18. In which of the following octahedral
4) Planar triangle complexes complexes of cobalt (atomic number = 27) will
EFFECTIVE ATOMIC NUMBER the magnitude of ∆ 0 be the highest ?
12. Stable complex based on EAN rule
3− 3+
1) Co (C2O4 )3 2) Co ( H 2O )6
1) K 4 Fe (CN )6 2) Co ( NH 3 )5 Cl Cl2
3+ 3−
3) Co ( NH 3 )6 4) Co (CN )6
3) Ni (CO )4 4) all the above
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COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
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19. If ∆0 < P , the correct electronic 8. IUPAC name of complex Cu ( NH 3 )4 SO4 is
configuration for d 4 system will be tetraamminecopper(II) sulphate.
( P =pairing energy)
12. EAN of Ni (CO )4 = 28 - 0 + 2 x 4 = 36, So it
1) t24g eg0 2) t23g e1g 3) t20g eg4 4) t22g eg2
is stable
APPLICATION OF COMPLEXES IN 13. It is outer orbital complex. Coordination
QUALITATIVE ANALYSIS AND METAL number is 4. Shape is tetrahedral.
CARBONYL COMPOUNDS AND STABILITY 18. Strength of ligands
OF CO-ORDINATION COMPOUNDS C2O4−2 < H 2O < NH 3 < CN −
20. Ammonium ions are detected with
1) Nessler’s reagent 2) Borsch reagent 19. Weak field ligand
3) Tollen’s reagent 4) Fehling’s solution 23. K = K1.K 2 .
21. ( Ph3 P )3 RhCl is a familiar catalyst used in
1) hydrogenation of oils LEVEL-I (H.W)
2) hydrogenation of alkenes
3) dehydration of alcohols WERNERS THEORY
4) dehydration of aldehydes 1. The complex formed by the combination of
22. Metals those can be extracted with aqueous calcium ions and ethylene di amine tetra
solution of sodium cyanide as complexes are
acetate. ( EDTA ) Number of moles of
−4
1) Au and Ag 2) Fe and Ag
3) Au and Hg 4) Hg and Fe calcium ions produced by disulving of one
23. Ag + NH 3 S Ag ( NH 3 ) ; K1 = 3.5 × 10
+ + −3 mole of that complex in excess of water is
+
1) one 2) two 3) four 4) five
A g ( N H 3 ) + N H 3 S A g ( N H 3 )2 ; K 2 = 1 .7 × 1 0 − 3
+
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7. Chelates are used in VBT AND SHAPES OF
1) Analytical chemistry 2) Water softning COORDINATION COMPOUNDS
3) Removal of Pb+2 from the blood 14. The following solutions requires three moles
of AgNO3 for the complete precipitation of
4) All of these all the chloride ions present in it
NOMENCLATURE 1) One litre of 1M [Co (NH3)6] Cl3
2) Three litres of 1M [Co (NH3)4 Cl2] Cl
8. Hexaaquotitanium ( III ) Chloride is 3) One litre of 1.5M [Co (NH3)5 Cl] Cl2
represented as 4) All the above
15. AgCl dissolved in excess of NH 3 , KCN and
1) Ti ( H 2 O )6 Cl3 2) [Ti Cl 3 ] 6H 2 O Na 2S 2O 3 solutions the complex produces
ions.
3) Ti ( H 2 O )5 Cl Cl2 4) Ti ( H 2 O )3 Cl3
+ − 3−
1. Ag ( NH3 )2 , Ag (CN )2 & Ag ( S2O3 )2
9. IUPAC name of Li[AlH4] is
2+ 3− 2+
1) Lithium aluminium hydride 2. Ag ( NH 2 )2 , Ag (CN )2 & Ag 4 ( S 2 O3 )5
2) Lithium tetrahydrido aluminate [III] 2+ + 2−
3. Ag ( NH 3 )2 , Ag (CN )2 & Ag 2 ( S 2 O3 )2
3) Tetrahydride aluminium lithionate
+ 3− 2−
4) Aluminium lithium hydride 4. Ag ( N H 3 )4 , Ag (C N )4 & Ag 2 ( S 2 O 3 )2
16. The secondary valency of chromium in
ISOMERISM
10. Dipole moment will be zero in the complexes Cr (en )3 Cl3 is
2− 1) 6 2) 3 3) 2 4) 4
1) Ni (CN )
4
CFT
2) Cis − Pt (NH 3 ) 2 Cl 2 17. Stabilisation energy of octahedral complex
with d 7 configuration
3) Trans − Pt (NH 3 ) 2 Cl 2 4) Both 1 and 3 A) 1.8 ∆ 0 with one unpaired electron
11. The number of geometrical isomers of B) 1.8 ∆ 0 with three unpaired electrons
Co ( NH 3 )3 ( NO3 )3 is
C) 0.8 ∆ 0 with one unpaired electron
1) 0 2) 2 3) 3 4) 4 D) 0.8 ∆ 0 with three unpaired electrons
+
12. For the given comlex CoCl2 (en )( NH 3 )2 , 1) A and D 2) A and B 3) C and D 4) B and C
18. If ∆ 0 > P , the correct electronic
the number of geometrical iosmers, the
number of optical isomers and total number confuguration for d 4 system will be ( p =
of isomers of all type possible respectively are pairining energy)
1) 2, 2 and 4 2) 2, 2 and 3 4 0
1) t2g eg 3 1
2) t2g eg 0 4
3) t2g eg 2 2
4) t2g eg
3) 2, 0 and 2 4) 0, 2 and 2
APPLICATION OF COMPLEXES IN
EFFECTIVE ATOMIC NUMBER QUALITATIVE ANALYSIS AND METAL
13. Which does not obey EAN rule? CARBONYL COMPOUNDS AND STABILITY
OF CO-ORDINATION COMPOUNDS
1) K 4 Fe (CN )6 2) K 3 Fe (CN )6 19. The ligand used in the identification of cupric
copper in the laboratory
3) Co ( NH 3 )6 Cl3 4) Ni (CO )4 1) NH 3 2) I − 3) CN − 4) S 2O32−
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COMPLEX COMPOUNDS JEE-MAIN-SR-CHEM-VOL-II
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20. The cofiguration of an element ‘X’ is 4 s1 3d 10 . ADDITIONAL QUESTIONS
The wrong statement regarding the element 1. Type of Pair of examples
‘X’ is isomerism
1) it forms complexes
A)Ionisation (a) Cr ( H 2O )6 Cl3 and
2) it exhibits variable velency
3) it forms paramagnetic ions only
Cr ( H 2O )5 Cl Cl2 .H 2O
4) It can form coloured salts
21. In the qualitative analysis of group 3 cations
Cr ( NH 3 )6 Co (CN )6
blood red colouration is a test for B) Linkage (b)
1) iron using cyanide as ligand & Co ( NH 3 )6 Cr (CN )6
2) chromium using cyanide as ligand
3) iron using thiocyanide as ligand Co ( NH 3 )5 ( NO2 ) Cl2
4) chromium using thiocyanide as ligand C)Coordination (c)
& Co ( NH 3 )5 (ONO ) Cl2
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4. COLUMN-I COLUMN-II 8. Match the lists I and II and pick the correct
(Complex) ( µ effective) matching from the codes given below
A) K3 [MnF6 ] p) 1.70 List - I List - II
(complex) (Structure and magneticmoment)
B) K3 [VF6 ] q) 2.8 −
a) Ag (CN )2 1) square planar and 1.73 BM
C) K2 [Mn(CN )6 ] r) 3.8
3−
D) K3 [TiF6 ] s) 4.9 b) Cu (CN )4 2) Linear and zero
A B C D A B C D 4−
c) Cu (CN )6 3) Octahedral and zero
1) s q r p 2) q s r p
3) s q p r 4) p q r s 2+
d) Cu ( NH 3 )4 4) tetrahedral and zero
5. Match the following.
Set -I Set -II 4−
e) Fe (CN )6 5) octrahedral and 1.73 BM
A) Co-ordination number 3 1) Pentagonal
bipyramidal 1) a-2,b-4,c-5,d-1,e-3 2) a-5,b-4,c-1,d-3,e-2
B) Co-ordination number 2 2) Trigonal 3) a-1,b-3,c-4,d-2,e-5 4) a-4,b-5,c-2,d-1,e-3
bipyramidal ASSERTION & REASON TYPE
C) Co-ordination number 5 3) Linear Two statements ‘A’ and ‘R’ are given below:
D) Co-ordination number 7 4) Trigonal planar Select your answers to these items using the
The correct matching is codes given below :
A B C D A B C D 1) Both A and R are correct and R is the correct
1) 4 3 2 1 2) 1 2 3 4 explanation of A
3) 4 3 1 2 4) 3 1 2 4 2) Both A and R are correct and R is not a correct
6. COLUMN-I COLUMN-II explanation of A
(Complex Ions) (No. of unpaired 3) A is true but R is false
electrons) 4) A is false but R is true
9. Assertion (A) : Among the cobalt (III)
A) [CrF6 ]4 − p)One 3+
complexes Co ( NH 3 )6 is a diamagnetic but
B) [MnF6 ] 4−
q) Two
[CoF6 ]
3−
is paramagnetic.
C) [Cr (CN )6 ]4 − r) Three
3+
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ISOMERISM
LEVEL-II (C.W)
7. The complexes Co ( NH 3 )6 Cr (C2O4 )3
DEFINITION OF and Cr ( NH 3 )6 Co (C2O4 )3
CO-ORDINATION COMPOUND 1) Geometrical isomerism
2) Ionization energy
1. Oxidation number of cobalt in K Co (CO )4 3) Co-ordination isomerism
is 4) Linkage isomerism
1) +1 2) +3 3) -1 4) -3 8. Which of the following complex or the
complex ion will show geometrical
[ EDTA]
4−
2. is a isomerism?
−
1) Monodentate ligand 2) Bidentate ligand 1) Pt ( NH 3 )2 Cl2 2) Pt ( NH 3 ) Cl5
3) Quadridentate ligand 4) Hexadentate ligand
3+
3. ‘en’ is an example of a 3) Pt ( NH 3 )5 Cl 4) Co ( NH 3 )6 Cl3
1) Monodentate ligand 2) Bidentate ligand 9. Which isomerism is exhibited by
3) Tridentate ligand 4) Hexadentate ligand Co ( NH 3 )3 ( H 2O )3 Cl3
NOMENCLATURE 1) Geometrical isomerism
2) Linkage isomerism
4. IUPAC name of K 2 [ PtCl6 ] is 3) Coordination isomerism
1) Potassiumhexachloroplatinum 4) Ionization isomerism
2) Potassiumhexachloroplatinum(IV) 10. Co ( NH 3 )4 ( NO2 )2 Cl exhibits
3) Potassium hexachloroplatinate(IV) 1) Linkage isomerism, ionization isomerism and
4) Dipotassium hexa chloro platinum geometrical isomerism
5. IUPAC name of 2) Ionisation isomerism, geometrical isomerism
and optical isomerism
Pt ( NH 3 )3 Br ( NO2 ) Cl Cl is 3) Linkage isomerism, geometrical isomerism
1) Triamminechlorobromonitroplatinum (IV) and optical isomerism
chloride 4) Linkage isomerism, ionization isomerism and
optical isomerism.
2) Triamminebromonitrochloroplatinum (IV)
11. Which one of the following is an example of
chloride
coordination isomerism?
3) Triamminebromochloronitroplatinum (IV)
chloride 1) Co ( NH 3 )5 Br SO4 and
4) Triamminenitrochlorobromoplatinum (IV) Co ( NH 3 )5 SO4 Br
chloride
6. Tetrammine diaqua copper (II) hydrox 2) Co ( NH 3 )5 NO2 Cl2 and
ide is given by the formula
Co ( NH 3 )5 ONO Cl2
1) Cu ( NH 3 )4 (OH )2 .2 H 2O
3) Cr ( H 2O )6 Cl3 and
2) Cu ( NH 3 )4 (OH )2 .2 H 2 O
Cr ( H 2O )5 Cl Cl2 .H 2O
3) Cu ( NH 3 )4 ( H 2O )2 (OH )2
4) Cr ( NH 3 )6 Co (CN )6 and
4) Cu ( NH 3 )4 ( H 2O )(OH )2 Co ( NH 3 )6 Cr (CN )6
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VBT CFT
20. For an octahedral complex, which of the
[ FeF6 ]
3+
12. has Fe atom .... hybridized with following d electron configuration will give
unpaired ........ electrons. maximum crystal - field stabilisation energy
1) d 2 sp 3 , 4 2) d 2 sp 3 ,5 1) High spin d 6 2) Low - spin d 4
3) sp 3 d 2 ,5 4) sp 3 d 2 ,3 3) Low spin d 5 4) High - spin d 7
13. How many EDTA molecules are required to APPLICATION OF COMPLEXES IN
make an octahedral complex with a Ca +2 QUALITATIVE ANALYSIS AND METAL
ion? CARBONYL COMPOUNDS AND STABILITY
1) two 2) six 3) three 4) one OF CO-ORDINATION COMPOUNDS
14. Which of the complexes will exhibit the 21. Chromium compound widely used in tanning
minimum paramagnetic behaviour of leather is
+2 +2 1) Cr2O3 2) Cr2O2Cl2 3) Cr2O3
1) Fe ( H 2O )6 2) Mn ( H 2O )6
4) K2 SO4Cr2 ( SO4 )3 24H 2O
+2 +2
3) Cr ( H 2O )6 4) Ni ( H 2O )6
22. Wilkinsons catalyst, Rh ( Ph3 P )3 Cl is used
15. The expected spin only magnetic moments for for
4−
Fe (CN )6 and [ FeF6 ] are
3− 1) Hydrogenation of oils
2) Hydrogenation of alkynes
1) 1.73and1.73 B.M 2) 1.73and 5.93 B.M 3) Hydrogenation of alkenes
3) 0.0 and1.73 B.M 4) 0.0 and 5.92 B.M 4) Polymerisation of alkenes
23. Coordination compounds have great
16. The volume (in mL) of 0.1M AgNO3 required importance in biological systems. In this
for complete precipitation of chloride ions context which of the following statements is
present in 30 mL of 0.01M solution of incorrect?
1) Chlorophylls are green pigments in plants and
Cr ( H 2O )5 Cl Cl2 as silver chloride is close contain calcium.
to 2) Haemoglobin is the red pigment of blood and
1) 3 2) 4 3) 5 4) 6 contains iron.
17. Among the following ions which one has the 3) Cyanocobalamin is B12 and contains cobalt.
highest paramagnetism: 4) Carboxypeptidase-A is an enzyme and
3+ 2+
1) Cr ( H 2O )6 2) Fe ( H 2O )6 contains zinc.
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6. Among the following which are ambidentate
LEVEL-III lignads ?
WERNER’S THEORY a) NO 2b) NO
−
c) EDTA
3
− 4-
Co ( NH 3 )5 Cl3 gives 3 moles of ions on 1) (a) and (b) 2) (c) and (d)
dissolution in water. One mole of the same 3) (a) and (f) 4) (a) and (e)
complex reacts with two moles of AgNO3 7. The number of donor sites in dimethyl
glyoxime, glycinato, diethylene triamine and
solution to yield two moles of AgCl ( s ) . The EDTA are respectively
structure of complex is 1)2,2,3 and 6 2) 2,2,3 and 4
1) Co ( NH 3 )4 Cl Cl2 .NH 3 3) 2,2,2 and 6 4) 2,3,3 and 6
2) Co ( NH 3 )5 Cl Cl2
NOMENCLATURE
8. The IUPAC name of the coordination
3) Co ( NH 3 )3 Cl3 2.NH 3
compound K 3 Fe (CN )6 is
4) Co ( NH 3 )4 Cl2 Cl.NH 3 1) potassium hexacyanoferrate (II)
2. The primary and secondary valencies of 2) potassium hexacyanoferrate (III)
chromium in the complex ion, 3) potassium hexacyanoiron (II)
dichlorodioxalatochromium (III), are 4) tripotassium hexacyanoiron(II)
respectively
1) 3,4 2) 4,3 3) 3,6 4) 6,3 ISOMERISM
3. In the complex with formula MCl3 .4 H 2O the 9. Which one of the following has largest
co-ordination number of the metal M is six number of isomers?
and there is no molecule of hydration in it. + 2+
1) Ru ( NH 3 )4 Cl2 2) Co ( NH 3 )5 Cl
The volume of 0.1M AgNO3 solution needed
2+ +
to precipitate the free chloride ions in 200ml 3) Ir ( Ph3 )2 H (CO ) 4) Co (en )2 Cl2
of 0.01M soltuion of the complex is
1) 40ml 2) 20 ml 3) 60 ml 4) 80 ml (R=alkyl group, en=ethylenediamine)
4. The molar ionic conductances of octahedral 10. Which of the following compounds shows
complexes. optical isomerism?
I) PtCl4 .5 NH 3 II) PtCl4 .4 NH 3 3− 3−
1) Cr (C2O4 )3 2) Co (CN )6
III) PtCl4 .3 NH 3 IV) PtCl4 .2 NH 3
2+
3) Cu ( NH 3 )4 4) [ZnCl4 ]
2−
1) I<II<III<IV 2) IV<III<II<I
3) III<IV<II<I 4)IV<III<I<II
11. In which of the following pairs both the
DEFINITION OF complexes do not show optical isomerism?
CO-ORDINATION COMPOUND −3
5. The coordination number of a central metal 1) cis − Cr (C2O4 )2 Cl2 ,
atom in a complex is determined by
1) the number of ligands around a metal ion trans − Co ( NH 3 )4 Cl2
bonded by sigma bonds
2) the number of ligands around a metal ion 2) Co ( en )3 Cl3 , Cis − Co (en )2 Cl2 Cl
bonded by π -bonds
3) PtCl2 ( en ) , [ NiCl2 Br2 ]
−2
3) the number of ligands around a metal ion
bounded by sigma and pi bonds both.
4) the number of only anionic ligands bonded 4) Co ( NO3 )3 ( NH 3 )3 , cis − Pt (en )2 Cl2
to the metal ion.
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12. Of the following configurations, the optical 17. The correct order of magnetic moments (spin
isomers are only values in bohr magneton) among is
4−
1) [MnCl4 ] > [CoCl4 ] > Fe (CN )6
2− 2−
4−
2) [MnCl4 ] > Fe (CN )6 > [CoCl4 ]
2− 2−
4−
3) Fe (CN )6 > [MnCl4 ] > [CoCl4 ]
2− 2−
4−
4) Fe (CN )6 > [CoCl4 ] > [MnCl4 ]
2− 2−
15. The complex K 3 Fe (CN )6 should have a hybridisation and magnetic moment of the
ions respectively are
spin only magnetic moment of
1) Tetrahedral ,square planar, octahedral :
1) 48BM 2) 2 5BM 3) 35BM 4) 6BM
sp3 , dsp 2 , sp3d 2 :5.9,0,4.9
16. Which one of the following complexes is an
outer orbital complex? 2) Tetrahedral ,square planar, octahedral :
4− 4− dsp 2 , sp3 , sp3d 2 :0,5.9,4.9
1) Fe (CN )6 2) Mn (CN )6
3) Square planar, tetrahedral ,octahedral :
3+ 2+
3) Co ( NH 3 )6 4) Ni ( NH 3 )6 dsp 2 , sp3 , d 2 sp 3 :5.9,4.9,0
4) Square planar, tetrahedral ,octahedral :
[Atomic numbers: Mn = 25, Fe = 26, Co = 27,
Ni = 28] dsp 2 , sp3 , sp3d 2 :0,5.9,4.9
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CFT 27. In Fe (CO )5 the Fe − C bond possess
22. Cr ( H 2O )6 Cl3 has a magnetic moment of 1) π − character only
3.83BM. The correct distribution of 3d 2) σ character only
electrons in chromium present in the complex 3) ionic character only
is 4) Both σ and π character
1
1
1) 3 d xy , 3 d 1yz , 3 d zx1 2) 3 d xy , 3 d 1yz , 3 d z12
LEVEL-III - KEY
1 1 1 1 1 1
3) 3d ( x2 − y 2 ) ,3d ,3d
4) 3d ,3d ( x2 − y 2 ) ,3d
z2 xz xy yz 1) 2 2) 3 3) 2 4) 2 5) 1 6) 4 7) 1
23. In which of the following octahedral 8) 2 9) 4 10) 1 11) 3 12) 3 13) 3 14) 2
complexes will the magnitude of ∆ 0 be the 15) 3 16) 4 17) 2 18) 3 19) 4 20) 4 21) 4
highest 22) 1 23) 1 24) 1 25) 1 26) 1 27) 4
3− 3−
1) Co (CN )6 2) Co (C2O4 )3
LEVEL-III - HINTS
3+ 2. 3+ Primary valecy corresponds to oxidation
3) Co ( H 2O )6 4) Co ( NH 3 )6
state and secondary valecy corresponds to
24. Which of the following is a correct Irving- coordination number primary=3, secondary=6.
Williams order? (Tendency of complex
formation) 3. Formula of complex is MCl2 ( H 2O )4 Cl .
1) Mn 2 + < Fe 2 + < Co 2 + < Ni 2 + Ionisable Cl − atoms are only one.
2) Ni 2 + < Co 2 + < Fe 2 + < Mn 2 + M1V1 = M 2V2
3) Fe 2 + < Mn 2 + < Ni 2 + < Co 2 + 4. IV of four complexes
2+
4) Co < Mn < Fe < Ni 2+ 2+ 2+
(1) is 3, (2) is 2, (3) is 1, (4) is 0
25. Which order is correct in spectrochemical 6. are ambidentate ligands which
− NO2 − and − SCN
series of ligands? have two donor atoms.
1) Cl − < F − < C2O42− < NO2− < CN −
The complex [Co(en) 2 Cl2 ] shows geometrical
+
9.
2) CN − < C2O42− < Cl − < NO2− < F − as well as optical isomerism.
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PREVIOUS AIEEE QUESTIONS 2. Aqueous solution of Ni contains [ Ni ( H 2 O )6 ]2 +
2+
1. Which one of the following has an optical and its magnetic moment is 2.83 B.M. when
isomer [AIEEE-2010] ammonia is added in it, the predicted change
2+ 2+ in the magnetic moment of solution is :
1) Zn (en )2
(
2) Zn en ( NH 3 ) )2 1) It will remain same
3+ 3+
2) It increases from 2.83 B.M.
3) Co (en )3 4) Co ( H 2O )4 en 3) It decreases from 2.83 B.M.
4) It can not be predicted theoretically.
2. Which of the following facts about the 3. Which of the following complexes is a
complex Cr ( NH 3 )6 Cl3 is wrong. paramagnetic complex ?
[AIEEE-2011] 1) K 2 Ni (CN )4 2) Ni ( H 2 O )6 ( NO3 ) 2
4) positive test for Fe 2+ , NH 4+ and SO42 − and magnetic moment is equal to n(n + 2) .
14. Complex compound is made up of 9. II and IV contain unpaired electrons.
1) simple cation and complex anion 10. The number of unpaired electrons in I, II, III &
2) complex cation and simple anion IV are 0, 1, 3 and 4 respectively.
3) complex cation and complex anion 11. The hybridisation is dsp 2 with one unpaired
4) all of these electron.
167