CCC 1

CO-ORDINATION COMPOUNDS

C1 Double Salts and Co-ordination Compounds

Double Salts : are those which loose their identity in solution as alum.
[K2SO4.Al2(SO4)3.24H2O]
Co-ordination Compounds (Complexes) : Those which retain their identity in solution
(complexes) as potassium ferrocyanide, K4[Fe(CN)6].
A complex (or co-ordination compound) is a compound consisting either complex ions
with other ions of opposite charge.
K4[Fe(CN)6] K+ is other ion
complex anion
[Pt(en)3]Cl4 Cl is other ion
complex cation
[Pt(en)2Cl2]
neutral complex
Ligands : A Ligand is a species that is capable of donating an electron pair(s) to a central
ion. It is a Lewis base. In accepting electron pairs, the central ion acts as a Lewis acid.
Ligand can be (a) unidentate
(b) bidentate, tridentate, tetradentate etc.
(c) Ambidient
Unidentate Ligand : Ligand is said to be unidentate if it has only one pair of electrons
that it can donate.
Polydentate Ligand : Ligand is said to be bidentate, tridentate, tetradentate etc.
depending on the number of electron pairs that it can donate.
(a) :NH3 ; one electron pair available for donation oxidentate.

(b) two electron pairs available for donation bidendate

Some common Multidentate Ligands (Chelating Agents)

Abbrevation Multi Name Formulae Charge

en bidentate ethylenediame 0

ox bidentate oxalate 2

gly bidentate glycinate 1

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 CCC 2
DMG bidentate dimethyl glyoximate 1

EDTA hexadentate ethylenediamine

tetraacetate 4
Chelates : Some ligands are capable of donating more than a single electron pair, from
different atoms in the ligand and to different sites in the geometric structure of a complex.
These are called as multidentate ligands. When the bonding of a multidentate ligand to
metal ion produces a ring (usually five or six membered) we refer to the complex as a
chelate. The multidentate ligand is called a chelating agent and the process of chelate
formation is called chelation

Nickel (II) dimethylglyoximate (chelate)

[bis-(dimethylglyoximato) nickel (II)]
Co-ordination Number : The co-ordination number of a metal atom in a complex is the
total number of bonds the metal atom forms with Ligands.
Co-ordination Number (C.N.) of Metal Ions
Metal ion C.N.
Ag+ 2
Cu+ 2, 4
Cu2+ 4, 6
Au+ 2, 6
Ca2+ 6
Fe2+, Fe3+ 6
Co2+ 4, 6
Co3+ 6
Ni2+ 4, 6
Zn2+ 4

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 CCC 3
Al3+ 4, 6
Sc3+ 6
Cr3+ 6
Pt2+ 4
Pt4+ 6
Complex C.N.
[Ag(NH3)2]+ 2
[HgI3] 3
[PtCl4]2, [Ni(CO)4] 4
[CO(NH3)6]3+ 6
Practice Problems :
1. FeSO4 solution mixed with (NH4)2SO4 solution in 1 : 1 molar ratio gives the test of Fe2+ ion but CuSO4
solution mixed with aqueous ammonia in 1 : 4 molar ratio does not give the test of Cu2+ ion. Explain
why ?
2. What is meany by unidentate, didentate and ambidentate ligands ? Give two examples for each.
3. Specify the oxidation numbers of the metals in the following coordination entities :
(i) [Co(H2O)(CN)(en)2]2+ (ii) [CoBr2(en)2]+
2
(iii) [PtCl4] (iv) K3[Fe(CN)6]
(v) [Cr(NH3)3Cl3]
4. What is meant by stability of a coordination compound in solution ? State the factors which govern
stability of complexes.
5. What is meany by the chelate effect ? Given an example.
6. How many ions are produced from the complex Co(NH3)6Cl2 in solution ?
(i) 6 (ii) 4 (iii) 3 (iv) 2
[Answers : (1) FeSO4 solution mixed with (NH4)2SO4 solution forms a double salt, which ionises in
the solution to give Fe2+ ions. CuSO4 solution mixed with aqueous ammonia forms a complex salt,
does not ionise to give Cu2+ ions (3) (i) +3 (ii) +2 (iii) +3 (iv) +3 (v) +3 (5) a didentate or a polydentate
ligand coordinates with the central metal ion forming a five or a six membered ring, the effect is
called chelate effect (6) (iii) is correct]

C2A Nomenclature : Following rules are adopted for naming a complex ion.
(a) cations are named before anions.
(b) oxidation state (O.S.) of the central metal ion is denoted by Roman numeral
Cation O.S. Anion
CuC2 Copper (II) chloride
FeCl3 Iron (III) chloride
(c) The names of ligands are given first followed by the name of central metal ion.
(d) The names of ligands that are anions and ending with
ide changed to o

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 CCC 4
ite changed to ito
ate changed to ato
(e) Some Common Unidentate Ligands
Neutral Anions (replacing ide by o)
Formula Names as Ligand Formula Name as Ligand
H2O aqua F(Fluoride) Fluorido
NH3 ammine Cl Chlorido
CO Carbonyl S2 sulphido
NO nitrosyl H hydrido
CH3NH2 methyl amine O2 (oxide) oxo
C5H5N or Py Pyridine OH (hydroxide) hydroxo
(C2H5)3N Triethylamine CN(cyanide) cyano*
(C6H5)3N Tripphenyl amine NC isocyano*
[* marked are ambident)
Replacing e by o
SO42 sulphato
S2O32 thiosulphato
CO32 carbonato
NO2 nitro*
ONO nitrito*
SCN thiocyanato*
NCS isothiocyanato*
(e) Positive groups end in-ium
NH2 NH3+ hydrazinium
(f) When there are several ligands of the same kind we normally use the prefix di, tri, tetra
soon. If the name of ligand includes a number e.g. ethylenediamine (en). To avoid
confusion in such cases, bis, trix and tetrakis are used.
e.g. bis (ethylenediammine)
(g) If anion is a complex then metal ends with ate [Ni(CN)4]2
tetracyanonickelate (II) ion
lead plumbate gold Aurate
tin stannate silver argentate
iron ferrate copper cuprate

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 CCC 5
(h) If the complex contain two or more metal atoms, it is termed polynuclear. The bridging
ligands which link the two metal atoms together are indicated by the prefix
(i) Ambidient Ligands may be attached through different atoms
M NO2 (NO2) joined to metal M through N; it is nitro
M ONO (NO2 joined to metal M through O it is nitro)
Similarly the SCN group may bond M-SCN (thiocyanato) or (M NCS) (isothiocyanato).
They may be named as
thiocyanato S, thiocyanato N
Practice Problems :
1. Write the IUPAC names of the following coordination compounds :
(i) [Co(NH3)6]Cl3 (ii) [Co(NH3)5Cl]Cl2 (iii) K3[Fe(CN)6]
(iv) K3[Fe(C2O4)3] (v) K2[PdCl4]
(vi) [Pt(NH3)2Cl(NH2CH3)]Cl
2. Using IUPAC norms, write the systematic names of the following :
(i) [Co(NH3)6]Cl3 (ii) [Pt(NH3)2Cl(NH2CH3)]Cl
3+
(iii) [Ti(H2O)6] (iv) [Co(NH3)4Cl(NO2)]Cl
2+
(v) [Mn(H2O)6] (vi) [NiCl4]2
(vii) [Ni(NH3)6]Cl2 (viii) [Co(en)3]3+
(ix) [Ni(CO)4]
[Answers : (1) (i) hexaamminecobalt(III) chloride (ii) pentaamminechloridocobalt(III) chloride (iii)
potassium hexacyanoferrate(III) (iv) potassium trioxalatoferrate(III) (v) potassium
tetrachloridopalladate(II) (vi) diamminechlorido (methylamine) platinum(II) chloride
(2) (i) hexaamminecobalt(III) chloride (ii) diamminechlorido(methyl amine)platinum(II) chloride
(iii) hexaaquatitanium(III) ion (iv) tetraamminechloridonitrito-N-cobalt(III) chloride (v)
hexaaquamanganese(II) ion (vi) tatrachloridonickelate(II) ion (vii) hexaamminenickel(II)
chloride (viii) tris(ethane-1, 2-diamine)cobalt(III) ion (ix) tetracarbonylnickel(0)]

C2B When writing (not naming) the formulae of the complex

complex ion should be enclosed by square brackets.
Ligands are place after metal in the alphabetical order but first negative ligands,
then neutral then positive.

[Pt (H 2 O) 4 (NH 3 ) 2 ] wrong

| |
aqua ammine

[Pt(NH3)2 (H2O)4] correct

[Cr (CN ) 4 ( NH 3 ) 2 ] correct

negative neutral

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 CCC 6
Example :-

1. K 4 [Fe(CN) 6 ]
cation Anion
Potassium hexacyanof errate(II)
cation anion

anion is complex hence metal ends with ate.

Ligands are named before metal ion of complex.

2. [CO( NH 3 ) 6 ] Cl 3
cation anion

Hexaammine cobalt (III) chloride

3. [CO(en)3]Cl3
Tris (ethylenediammine) cobalt (III) chloride
4. [Pt(Cl)2(NH3)4]Cl2
Tetraamminedichloroplatinum (IV) chloride
[NH3(ammine) and Cl(chloro) are written in alphabetical order]
5. In the following examples complex ion exist as cation :-
(a) [Fe(NH3)6]Cl3 Hexaammine iron (III) chloride
(b) [CoCl(NH3)5]2+ Pentaamminechlorocobalt (III) ion
(c) [CoSO4(NH3)4]NO3 Tetraamminesulphatocobalt (III) nitrate
6. Complex ion exist as anions :-
(a) [ZnCl4]2 Tetrachlorozincate (II) ion
(b) [AlH4] Tetrahydridoaluminate (III) ion
(c) Na3[Ag(S2O3)2] Sodium bis (thiosulphato) argentate (I)
(d) Na2 [OSCl5N] sodium pentachloronitrido osmate (VI)
(e) K2[Cr(CN)2O2(O2)NH3] Potassium amminedicyanodioxo peroxochromate (VI)
7. Organic Ligands have been used :-
(a) [Pt(Py)4] [Pt Cl4] Tetrapyridineplatinum (II) tetrachloroplatinate (II)
(b) [Cr(C6H6)2] Bis (benzene) chromium (O)
(c) [Fe(C5H5)2] Bis (cyclopentadienyl) iron (II)
8. In the following examples, bridging groups are used :-

(a)

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 CCC 7
Tetrakin (ethylenediammine)--imido--hydroxo dicobalt (III) ion.

Trans-bis (chlortiphenylphosphine--chloropalladium (II)

or
Chlorotriphenylphosphinepallodium (II)--dichlorochlorotriphenylphosphinepalladium (II)
Practice Problems :
1. Write the formulas for the following coordination compounds :
(i) Tetraamminediaquacobalt(III) chloride
(ii) Potassium tetracyanonickelate(II)
(iii) Tris(ethane-1, 2-diamine) chromium(III) chloride
(iv) Amminebromidochloridonitrito-N-platinate(II)
(v) Dichloridobis(ethane-1, 2-diamine)platinum (IV) nitrate
(vi) Iron (III) hexacyanoferrate (II)
2. Using IUPAC norms write the formulas for the following :
(i) Tetrahydroxozincate(II) (ii) Potassium tetrachloridopalladate(II)
(iii) Diamminedichloridoplatinum(II) (iv) Potassium tetracyanonickelate(Ii)
(v) Pentaaminenitrito-O-cobalt(III) (vi) Hexaamminecobalt(III) sulphate
(vii) Potassium trioxalatochromate(III) (viii) Hexaammineplatinum(IV)
(ix) Tetrabromidocuprate(II) (x) Pentaamminenitrito-N-cobalt(III)
[Answers : (1) (i) [Co(NH3)4(H2O)2]Cl3 (ii) K2[Ni(CN)4] (iii) [Cr(en)3]Cl3 (iv) [PtBrClNO2(NH3)]
(v) [PtCl2(en)2](NO3)2 (vi) Fe 4[Fe(CN) 6] 3 (2) (i) [Zn(OH) 4] 2 (ii) K 2[PdCl 4] (iii) [Pt(NH 3 ) 2 Cl 2 ]
(iv) K2[Ni(CN)4] (v) [Co(NH3)5(ONO)]2+ (vi) [Co(NH3)6]2(SO4)3 (vii) K3[Cr(C2O4)3] (viii) [Pt(NH3)6]4+
(ix) [CuBr4]2 (x) [Co(NH3)5(NO2)]2+]

C2C (EAN) Effective Atomic Number :

Each ligand donates an electron pair to the metal ion, thus forming a co-ordinate bond
EAN = Z O.N. + 2 (C.N.)
ON oxidation number
or C.N. co-ordination number
EAN = Z O.N. + 2 (Ligands)
(assuming that each ligand is unidentate)
Example :-
(a) [Cr(CO)6] EAN = 24 O + 2 6 = 36
(b) [Fe(CN)6]2 EAN = 26 2 + 6 2 = 36
(c) [CO(en)3]3+ EAN = 27 3 + 6 2 = 36
(en) bidentate
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 CCC 8
Practice Problems :
1. Explain with two examples each of the following : coordination entity, ligand, coordination number,
coordination polyhedron, homoleptic and heteroleptic.

C3 Isomerism in Complexes :-
Compounds having same chemical formulae but differ structural arrangements are called
isomers.
Structural isomerism :-
Differ from each other. How the atoms are joined together that is in the order in which the
atoms are bonded to each other.
H N = C = O and N C O H are structural isomer.
Ionisation Isomerism :-
This type of isomerism occurs when there is an interchange of groups between the
co-ordination sphere of the metal ion and the ions outside this sphere. Examples are :
(a) [CO(NH3)5 (SO4]Br [CO(NH3)5Br] SO4
[give yellow ppt. with Ag+] [give white ppt. with Ba 2+ as SO 4 2 being
ion as Br outside the bracket ionisable]
is ionisable]

(b) [Pt(NH3)4Cl2] Br2 [Pt(NH3)4Br2] Cl 2

ionisable ionisable

Co-ordination isomerism :-
When both positive and negative ions are complex ions. Isomerism may be caused due to
interchange of ligands between anion and cation. This arises only when cation and anion
have same C.N. and charge
(a) [CO(NH3)6]3+ [Cr(CN)6]3 same charge
&
[Cr(NH3)6]3+ [CO(CN)6]3 same O.N.
Linkage Isomerism :-
(i) [CO(NH3)5ONO]Cl2 and [CO(NH3)5NO2]Cl2
(ii) [Mn(CO)5 (SCN)]+ [Mn(CO)5(NCS)]+
Co-ordination Position Isomerism :
In polynuclear complexes an interchange of ligands between the different metal nuclei
give rise to positional isomerism e.g.

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 CCC 9

Hydrate Isomerism :-
Hydrate isomers of a complex that differ in the placement of water molecules in the com-
plex CrCl3.6H2O can be written as
[Cr(H2O)6]Cl3 violet (anhydrous)
[Cr(H2O)5Cl]Cl2.H2O light green (monohydrate)
[Cr(H2O)4Cl2]Cl.2H2O Dart green (dihydrate)
Stereo Isomers :-
1. Geometrical
2. Optical
Geometrical :- are isomers in which the atoms are joined to one another in the same way
but differ because some atom occupy different relative position in space.
Geometrical Isomers of C.N. 4
(a) [Pt(NH3)2Cl2]

(b)

Geometrical isomers of C.N. 6

(a) [CO(NH3)4Cl2]+

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 CCC 10

(b) [Pt(NH3)Cl2Br2]

(c) [Pt(NH3)3Cl3]

Optical Isomerism :- If a molecule is asymetric that it cannot superimposed on its mirror

image. The two forms have the same type of symmetry shown by the left and right hands
and are called enantiomeric pair. The two forms are called optical isomers. They are called
either dextro or leavo (dor l).
Optical isomerism is common in octahedral complexes involving bidentate ligands.
[CO(en)2Cl2] exists as cis and trans but cis-form can have optical isomerism.

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 CCC 11

Practice Problems :
1. Give evidence that [Co(NH3)5Cl]SO4 and [Co(NH3)5SO4]Cl are ionisation isomers.
2. List various types of isomerism possible for coordination compounds, giving an example of each.
3. How many geometrical isomers are possible in the following coordination entities ?
(a) [Cr(C2O4)3]3 (b) [Co(NH3)3Cl3]
4. Draw the structures of optical isomers of :
(a) [Cr(C2O4)3]3 (b) [PtCl2(en)2]2+
(c) [Cr(NH3)2Cl2(en)]+
5. Draw all the isomers (geometrical and optical) of :
(i) [CoCl2(en)2]+ (ii) [Co(NH3)Cl(en)2]2+
(iii) [Co(NH3)2Cl2(en)]+
6. Write all the geometrical isomers of [Pt(NH3)(Br)(Cl)(py)] and how many of these will exhibit
optical isomers ?

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 CCC 12
[Answers : (1) On dissolving in water, the two compounds will give different ions in the solution
which can be tested by adding AgNO3 solution and BaCl2 solution (3) (a) no possibility (b) two
geometrical isomers (6) Three isomers are possible]

C4A Werners theory of co-ordination compounds :

1. There are two types of valency shown by central metal atom/metal ion in a compound
(a) Primary (b) Secondary
Primary Valency corresponds to oxidation number and secondary valency corresponds
to co-ordination number.
In the complex [CO(NH3)6]Cl3, primary valency is satisfied by three Cl, secondary
valency is six.
In [CO(NH3)4(H2O)2]SO4, four NH3 and two H2O (ligands) satisfy secondary valency.
One SO42 satisfy primary valency.
Primary valency is ionisable.
The secondary valencies are directional and are responsible for isomerism in complexes.
The primary valencies are non-directional and is represented by ..... and secondary
valency by _______________
In all cases, metal or metal ions should satisfy primary and secondary valency both. Some
negative ions can satisfy primary as well as secondary valency both.
e.g. [Cr(NH3)5Cl]Cl2 satisfy both primary and secondary valency.
Practice Problems :
1. Explain the bonding in coordination compounds in terms of Werners postulates.

C4B Bonding in complexes

The metal m loses required no. of electrons to form cation. No. of electrons lost corre-
spond to O.N.
The metal ion makes available a no. of empty orbitals equal ot its co-ordinates number for
the formation of co-ordinates bonds with the Ligand Orbitals.
A weak ligand like (H2O, halide) will not affect the electronic configuration of the metal/
metal ion.
A strong ligand like (NH3, CN, CO) affect the electronic configuration of the metal/
metalion. They make unpaired electrons paired.
The metal ion orbitals hybridise to form a new set of equivalent hybridised orbitals.
If there are unpaired electrons in the complex it is called paramagnetic.

Magnetic moment = N( N 2) B.M.

N no. of unpaired electrons.

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 CCC 13
The complex with so many unpaired electrons is high spin complex and that with paired
electrons is low spin complex.
If inner d-orbital is used for hybridisation it is called inner d complex. e.g. d2sp3 [Fe(CN)6]4
If outer d-orbital is used is called outer d-complex. sp3d2
Weak field ligand [Fe(H2O)6]3+
I < Br < S2 < Cl < NO3 < F < oxalate < H2O < EDTA < NH3 < en < NO2 < CN
< CO
Examples : [Fe(CN)6]4 O.N. = +2
C.N. = 6
[six empty orbitals are required by six CN ligands] t2g dxy, dyz, dzx e.g. dx2 y2, dz2

Complex ion is d2sp3 hybridised Inned d-complex

Diamagnetic Magnetic moment = O
Octahedral geometry
[Fe(H2O)6]3+

(H2O is weak ligand)

Hybridisation sp3d2 Outer-d-complex
Paramagnetic (High spin complex) Octahedral geometry

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 CCC 14
Commom type of hybridisation and Geometry of complexes
Hybridisation Geometry Examples
sp Linear [Ag(NH3)2]+
sp2 Trigonal Planal [HgI3], [CuP(Me)3]+
sp3 Tetrahedral [VO4]3, [MnO4],
[NiCl4]2, [Ni(CO)4],
[Zn(Cl4)]2
dsp2 Square planar [Cu(NH3)4]2+,
[Ni(CN)4]2,
[Pt(NH3)4]2+
sp3d or dsp3 Trigonal [Cu(Cl5)]3, [Ni(CN)5]3
d2sp3 or Bipyramidal [Fe(CO)5]
sp3d2 Octahedral [Fe(H2O)6]3+
Practice Problems :
1. Explain on the basis of valence bond theory that [Ni(CN)4]2 ion with square planar structure is
diamagnetic and the [NiCl4]2 ion with tetrahedral geometry is paramagnetic.
2. [NiCl4]2 is paramagnetic while [Ni(CO)4] is diamagnetic though both are tetrahedral. Why ?
3. Explain [Co(NH3)6]3+ is an inner orbital complex whereas [Ni(NH3)6]2+ is an outer orbital complex.
4. Predict the number of unpaired electrons in the square planar [Pt(CN)4]2 ion.
5. The hexaaquo manganese (II) ion contains five unpaired electrons while the hexacyanoion contains
only one unpaired electron. Explain using Crystal Field Theory.
6. Aqueous copper sulphate solution (blue in colour) gives :
(i) a green precipitate with aqueous potassium fluoride and
(ii) a bright green solution with aqueous potassium chloride.
Explain these experimental results.
7. What is the coordination entity formed when excess of aqueous KCN is added to an aqueous
solution of copper sulphate ? Why is it that no precipitate of copper sulphide is obtained when
H2S(g) is passed through this solution ?
8. Discuss the nature of bonding in the following coordination entities on the basis of Valence Bond
Theory :
(i) [Fe(CN)6]4 (ii) [FeF6]3 (iii) [Co(C2O4)3)]3 (iv) [CoF6]3
9. Draw a figure to show the splitting of d-orbitals in an octahedral crystal field.
10. What is spectrochemical series ? Explain the difference between a weak field ligand and a strong
field ligand.
11. What is crystal field splitting energy ? How does the magnitude of 0 decide the actual configuration
of d-orbitals in a coordination entity ?
12. [Cr(NH3)6]3+ is paramagnetic while [Ni(CN)4]2 is diamagnetic. Explain, why ?
13. A solution of [Ni(H2O)6]2+ is green but a solution of [Ni(CN)4]2 is colourless. Explain.
14. [Fe(CN)6]4 and [Fe(H2O)6]2+ are of different colours in dilute solutions. Why ?
15. Discuss the nature of bonding in metal carbonyls.

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16. Write down the IUPAC name for each of the following complexes and indicate the oxidation state,
electronic configuration and coordination number. Also give stereochemistry and magnetic moment
of the complex :
(i) K[Cr(H2O)2(C2O4)2].3H2O (ii) CrCl3(py)3
(iii) [Co(NH3)5Cl]Cl2 (iv) [Cs[FeCl4]
17. Discuss briefly giving an example in each case the role of coordination compounds in :
(i) biological systems (ii) medicinal chemistry
(iii) analytical chemistry and (iv) extraction/metallurgy of metals
18. Amongst the following ions, which one has the highest magnetic moment value ?
(i) [Cr(H2O)6]3+ (ii) [Fe(H2O)6]2+ (iii) [Zn(H2O)6]2+
19. The oxidation number of cobalt in K[Co(CO)4] is
(i) +1 (ii) +3 (iii) 1 (iv) 3
20. Amongst the following, the most stable complex is :
(i) [Fe(H2O)6]3+ (ii) [Fe(NH3)6]3+ (iii) [Fe(C2O4)3]3 (iv) [FeCl6]3
21. What will be the correct order for the wavelengths of absorption in the visible region for the
following : [Ni(NO2)6]4, [Ni(NH3)6]2+, [Ni(H2O)6]2+
[Answers : (2) Cl is weak ligand. It cannot pair up the electrons in 3d orbitals. Presence of strong
CO ligand and 4s electrons shift to 3d to pair up with 3d electrons (3) Presence of NH3 pairing of 3d
electrons takes place leaving two d-orbitals empty. In [Ni(NH3)6]2+, Ni is in +2 state with the
configuration 3d8. The NH3 can not pair up 3d electrons (4) No unpaired electron (6) (i) weak H2O
ligands are replaced by F ligands forming [CuF4]2 ions which is a green precipitate (ii) weak H2O
ligands are replaced by Cl ligands forming [CuCl4]2 ion which has bright green colour (7) The
complex ion is highly stable and does not dissociate to give Cu2+ ions. Hence, no precipitate with H2S
is obtained (8) (i) d2sp3 (ii) sp3d2 (iii) d2sp3 (iv) sp3d2 (10) ligands in order of their increasing field
strengths (11) The difference of energy between the two sets of orbitals is called crystal field splitting
4 0
energy. If 0 < P, then 4th electron pairsup in one of the t2g orbitals giving the configuration t 2g e g
thereby forming low spin complexes (13) In [Ni(H 2O) 6] 2+, it has two unpaired electrons.
In [Ni(CN)4]2, no unpaired electrons (14) ligands H2O and CN possess different crystal field
splitting energy (0) (18) (ii) having greatest value of n has highest magnetic moment (19) (iii) is the
correct option (20) (iii) is correct option (21) Ni(H2O)6]2+ > [Ni(NH3)6]2+ > [Ni(NO2)6]4]

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 State of Hybridisation and Magnetic Behaviour of some co-ordination complex
CCC 16

Hybridisation

Unit No. 102, 103, Vardhman Ring Road Plaza, Vikas Puri Extn., Outer Ring Road
Metal Metal Configuration of metal ion No. of unpaired Magnetic
Complex Ion of metal ion orbitals for electrons Behaviour
ligand bonds
[V(H2O)6]3+ V3+ d2 sp3d2 2 Paramagnetic
[Cr(NH3)6]3+ Cr3+ d3 d2sp3 3 Paramagnetic

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[MnF6]3 Mn3+ d4 sp3d2 4 Paramagnetic
[Mn(CN)6]3 Mn3+ d4 d2sp3 2 Paramagnetic
[Fe(CN)6]3 Fe3+ d5 d2sp3 1 Paramagnetic
[Fe(F6)]3 Fe3+ d5 sp3d2 5 Paramagnetic
[Fe(Cl4)]2 Fe2+ d6 sp3 4 Paramagnetic
[COF6]3 CO3+ d6 sp3d2 4 Paramagnetic
[CO(CN)6]3 CO3+ d6 d2sp3 0 Diamagnetic
[Ni(Cl)4]2 Ni2+ d8 sp3 2 Paramagnetic
[Ni(CN)4]2 Ni2+ d8 dsp2 0 Diamagnetic

Einstein Classes,
[COCl4]2 CO2+ d9 sp3 1 Diamagnetic
[Zn(NH3)4]2+ Zn2+ d10 sp3 0 Diamagnetic
 CCC 17
E X E R C I S E (OBJECTIVE)

1. The EAN of Ni in Ni(CN)42 is 11. Hexafluorocobaltate (III) ion is found to be high

spin complex, the probable hybrid state of cobalt
(a) 34 (b) 35
in it is
(c) 36 (d) 28
(a) d2sp3 (b) sp3
2. Glycinato ligand is
(c) sp3d (d) sp3d2
12. In sodium tetrafluorooxochromate(.....),
(a) Na3[Cr(O)F4] the left out place should be filled with
which of the following Roman numericals
(b) Bidentate ligand
(a) VI (b) III
(c) Two donor sites N and O
(c) IV (d) none of these
(d) All
13. The correct name of the compound
3. The compound which does not show [Cu(NH3)4](NO3)2, according to IUPAC system is
paramagnetism
(a) Cuprammonium nitrate
(a) [Cu(NH3)4]Cl2 (b) [Ag(NH3)2Cl
(b) Tetraammine copper(II) dinitrate
(c) NO (d) NO2
(c) Tetraammine copper(II) nitrate
4. Which one is bidentate ligand
(d) Tetraammine copper(I) dinitrate
(a) C2O42
14. Lithium tetrahydridoaluminate is correctly
(b) NH2CH2CH2NH2 represented as
(c) Both (a) Al[LiH4] (b) Al2[LiH4]3
(d) None (c) Li[AlH4] (d) Li[AlH4]2
5. Which ion is paramagnetic 15. The correct IUPAC name of K2[Zn(OH)4] is
(a) [Co(NH3)4]2+ (b) [Ni(CO)4] (a) Potassium tetrahydroxyzinc(II)
(c) [Co(NH3)6]3+ (d) [Ni(CN)4]2 (b) Potassium tetrahydroxozincate(II)
6. The shape of the complex Ag(NH3)2+ is (c) Potassium tetrahydroxyzincate(IV)
(a) Octahedral (b) Square planar (d) Potassium hydroxozinc(II)
(c) Tetrahedral (d) Linear 16. The correct IUPAC name of KAl(SO4)3 12H2O is
7. K3CoF6 is high spin complex. What is the hybrid (a) Aluminium potassium sulphate-12-water
state of Co atom in this complex
(b) Potassium aluminium(III) sulphate-12-
(a) sp3d (b) sp3d2 water
(c) d2sp3 (d) dsp2 (c) Potassium aluminate(III) sulphate
8. Which one of the following will be able to show hydrate
cis-trans isomerism (d) Aluminium(III) potassium sulphate
hydrate-12
(a) MA3B (b) M(A A )2
17. Number of electrons gained by Pd in [PdCl4]2;
(c) MA2BCD (d) MA4
(a) 4 (b) 8
9. The type of isomerism shown by [Co(en)2(NCS)2]Cl
and [Co(en)2(NCS)Cl]NCS is (c) 10 (d) Zero
(a) Co-ordination (b) Ionisation 18. The possible number of isomers for the complex
[MCl2Br2]SO4 is
(c) Linkage (d) All above
(a) 1 (b) 2
10. Which of the following cations does not form an
amine complex with excess of ammonia (c) 4 (d) 5
(a) Ag+ (b) Cu2+ 19. The oxidation number of Pt in [Pt(C2H4)Cl3] is
(c) Cd2+ (d) Na+ (a) +1 (b) +2
(c) +3 (d) +4

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 CCC 18
20. Chlorophyll is a co-ordination compound having (b) Presence of water molecule
central atom of (c) Excitation of electrons from d d
(a) Ca (b) Mg (d) Intramolecular vibration
(c) Na (d) K 29. The number of d-electrons in [Cr(H2O)6]3+ is
2 2
21. Among [Ni(CN)4] [NiCl4] and [Ni(CO)4] (a) 2 (b) 3
(a) Ni(CN)22 is square planar and NiCl42 (c) 4 (d) 5
and Ni(CO)4 are tetrahedral
30. Ammonia forms the complex ion [Cu(NH3)4]2+ with
(b) NiCl42 is square planar and Ni(CN)42 copper ions in alkaline solutions but not in acidic
and Ni(CO)4 are tetrahedral solutions. What is the reason for it ?
(c) Ni(CO)4 is square planar and Ni(CN)42 (a) Copper hydroxide is an amphoteric
and [NiCl4]2 are tetrahedral substance
(d) None (b) In acidic solution hydration protects
22. Which one does not belong to ligand copper ions
(a) PH3 (b) NO+ (c) In acidic solutions protons coordinates
(c) BF3 (d) Cl with ammonia molecules forming NH4+
ions and NH3 molecules are not available
23. Nickel metal is in highest oxidation state in
(d) In alkaline solution insoluble Cu(OH)2 is
(a) Ni(CO)4 (b) K2NiF6 precipitated which is soluble in excess
(c) [Ni(NH3)6](BF4)2(d) K4[Ni(CN)6] of any alkali
24. A complex of cobalt has five ammonia molecules, 31. In the coordination compound, K4[Ni(CN)4], the
one nitro group and two chlorine atoms for each oxidation state of nickel is
cobalt atom. One mole of this compound produces (a) +2 (b) 1
three moles ions in aqueous solution which on
treating with excess of AgNO3 give two moles of (c) 0 (d) +1
AgCl. The formula of the compound is 32. The coordination number of a central metal atom
(a) [Co(NH3)4NO2Cl][(NH3)Cl] in a complex is determined by
(b) [Co(NH3)5Cl][ClNO2] (a) the number of ligands around a metal ion
bounded by sigma bonds
(c) [Co(NH3)5NO2]Cl2
(b) the number of ligands around a metal ion
(d) [Co(NH3)5][(NO2)2Cl2] bounded by pi-bonds
25. K3[Al(C2O4)3] is called (c) the number of ligands around a metal ion
(a) Potassium alumino oxalate bonded by sigma and pi-bonds both
(b) Potassium alumino (III) oxalate (d) the number of only anionic ligands
(c) Potassium trioxalato aluminate bonded to the metal ion.
(d) Potassium trioxalato aluminate (III) 33. Which one of the following complexes is an outer
orbital complex ?
26. In hexacyanomanganate (II) ion the Mn atom
assumes d2sp3 hybrid state. The number of unpaired (a) [Fe(CN)6]4 (b) [Mn(CN)6]4
electrons in the complex is (c) [Co(NH3)6]3+ (d) [Ni(NH3)6]2+
(a) 1 (b) 2 [Atomic nos. : Mn = 25, Fe = 26, Co = 27, Ni = 28]
(c) 3 (d) zero 34. Cerium (Z = 58) is an important member of the
27. Name the metal M which is extracted on the basis lanthanoids. Which of the following statmenets
of following reactions about cerium is incorrect ?
4M + 8CN + 2H2O + O2 4[M(CN)2] + 4OH (a) The common oxidation states of cerium
are +3 and +4
2[M(CN)2] + Zn [Zn(CN)4]2 + 2M
(b) The +3 oxidation state of cerium is more
(a) Nickel (b) Silver
stable than +4 oxidation state
(c) Copper (d) Mercury
(c) The +4 oxidation state of cerium is not
3+
28. The colour of [Ti(H2O)6] is due to known in solutions
(a) Transfer of an electron from one Ti to (d) Cerium (IV) acts as an oxidising agent.
another

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 CCC 19
35. The correct order of magnetic moments (spin only 40. The IUPAC name for the complex
values in B.M.) among is [Co(NO2)(NH3)5]Cl2 is
(a) [MnCl4]2 > [CoCl4]2 > [Fe(CN)6]4 (a) pentaamminenitrito-N-cobalt(III)
(b) 2
[MnCl4] > [Fe(CN)6] > [CoCl4] 4 2 chloride
(c) [Fe(CN)6]4 > [MnCl4]2 > [CoCl4]2 (b) nitrito-N-pentaamminecobalt(III)
chloride
(d) [Fe(CN)6]4 > [CoCl4]2 > [MnCl4]2
(c) nitrito-N-pentaamminecobalt(II)
36. The IUPAC name of the coordination compound chloride
K3[Fe(CN)6] is
(d) pentaamminenitrito-N-cobalt(II)
(a) Potassium hexacyanoferrate (II) chloride
(b) Potassium hexacyanoferrate (III) 41. Nickel (Z = 28) combines with a uninegative
(c) Potassium hexacyanoiron (II) monodentate ligand X to form a paramagnetic
(d) Tripotassium hexacyanoiron (II) complex [NiX 4 ] 2 . The number of unpaired
electron(s) in the nickel and geometry of this
37. Which of the following compounds shows optical
complex ion are, respectively
isomerism ?
(a) two, square planar
(a) [Cu(NH3)4]2+ (b) [ZnCl4]2
(b) one, tetrahedral
(c) [Cr(C2O4)3]3+ (d) [Co(CN)6]3
(c) two, tetrahedral
38. Which one of the following cyano complexes would
exhibit the lowest value of paramagnetic (d) one, square planar
behaviour ? 42. In Fe(CO)5, the Fe-C bond possesses
3 3
(a) [Cr(CN)6] (b) [Mn(Cn)6] (a) -character only
3 3
(c) [Fe(CN)6] (d) [Co(CN)6] (b) -character only
[At. Nos : Cr = 24, Mn = 25, Fe = 26, Co = 27) (c) both and characters
39. The value of the spin only magnetic moment for (d) ionic character
one of the following configurations is 2.84 BM. The 43. The spin-only magnetic moment [in units of Bohr
correct one is magneton. (B)] of Ni2+ in aqueous solution would
(a) d4 (in strong ligand field) be (atomic number Ni = 28)
(b) d4 (in weak ligand field) (a) 1.73 (b) 2.84
(c) d3 (in weak as well as in strong field) (c) 4.90 (d) 0
(d) d5 (in strong ligand field) 44. How many EDTA (ethylenediaminetetraacetic acid)
molecules are required to make an octahedral
complex with a Ca2+ ion ?
(a) Two (b) Six
(c) Three (d) One

ANSWERS
1. a 9. b 17. b 25. d 33. d 41. c
2. d 10. d 18. d 26. a 34. c 42. c
3. b 11. d 19. b 27. b 35. a 43. b
4. c 12. b 20. b 28. c 36. b 44. d
5. a 13. c 21. a 29. b 37. c
6. d 14. c 22. c 30. c 38. c
7. b 15. b 23. b 31. c 39. a
8. c 16. b 24. c 32. a 40. a

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New Delhi 110 018, Ph. : 9312629035, 8527112111