An Introduction to Coordination Compounds 123

Exercise

Fieein tAe Beanks

1. NO2 is an... igand.
2. Diethylenetriamine is a ... ligand.
3. Coordination number of Mo in [Mo(CN)8
1*
4. The oxidation number
of Fe in [Fe(H,0)5 (NO)]** IS...... .*
5. In the complex [Co(en)3 ]°* en is. . .
,
igand.
6. In the complex
[Ce(NOs)%. NOJ behaves ligand.
7. In the complex [Co(en)2(NO, NO; )]*. NO is an igand whereas NOj is not an
... igand.
8. Hemoglobin is a type of. *******
.Complex.

9. Pyrazine is a .. . aswell aas igand.

10. EDTA* is a .. ligand.
11. The molar conductance of[Co(NH3 )% ]Cl3 is.**********
. than that of [Co(NH3)5CI]Cl2.
12. Ethylenediamine is a . . . . as wvell as . ***** ******** ligand.
13. Gly (NH2CH2CO0)is an ......... ***** as well as. ... ligand.

14. The complex [Co(en):P" is a type of .

15. The magnitude of depression in freezing point of Im aqueous solution of [Co(NH3)5 CI]Cl2 is
********..than that of Im aqueous of solution of[Co(NH,)4 Cl2 ]CL
16. The primary and secondary valencies in [Co(NH3)5CI]Cl2 are .. al0 ..... **

respectively.
17. The complex [FeeCN6F . 18 electron nule

18. The complex [Co(NH;)%1°*.. ... EAN rule.

[Ans. 1. ambidentate 2. tridentate or chelating
3. 8 4. +1
5. bidentate 6. bidentate
ambidentate, ambidentate 8. macrocyclic
9. monodentate, bridging 10. hexadentate (chelating)
11. greater 12. symmetric, bidentate
13. unsymmetric, bidentate 14. chelate
15 greater 16. 3,6
17. does not obey 18. obey
 Coordination Chemistry
.24
06jective Questions
1. Which of thefollowing ligands does not behave as ambidentate ligand?
(a) NOZ (b)-SCN

)S20 (d) NO
2. Which of the following ligands behaves as an ambidentate ligand?
(a) NO (b) SO
(c) SOg (d) CI04
3. The oxidation state of Rh in (NH4)3 (RhCI,) is:
(a) +1 (b) +2
(c) +3 (d)+6
4. Which of the following ligands beahves as a flexidentate ligand?
(a) NO (b) SCN
(c) CNO (d) OH
5. Oxidation number of W in MgWO4 is:
(a) +2 (b) +3

c)+4 (d)+6
6. A ligand in metal complexes behaves as:
(ii) Lewis base
(i) pair donor
electron
(in) nucleophile (iv) electrophile
(a) (i) and (i) only (b) (i) and (ii) only
(c) i), (i) and (ii) only (d) All of the above
transition metal complexes is
7. The ligand that exhibits linkage isomerism in its
(a) [sO31 (b) [SO41
(c) [NO] (d) [ClO4
8. Which ofthe following is not a chelating ligand?
(b) Oxalato
(a) Thiosulphato
(c) Glycinato (d) Ethylenediamine
9. A compound contains 1.08 mol of Na, 0.539 mol of
Cu and 2.166 mol of F. Its aqueous solution
shows osmotic pressure which is three times that of urea having same molar concentration. The
formula of the compound is:
(a) Na4[CuF6] (b) Na[CuF41
c) Na2[CuF4 ] (d) Na2[CuF3]
10. The three dimensional structure of compound [Co(Co(NH3)4 (OH)2)3 JBr6 has

(a) twelve Co-O and twelve Co-N bonds

(b) ten Co-0 and ten Co-N bonds
(c) Fourteen Co-O and ten Co-N bonds
(d) twelve Co-0 and ten Co-N bonds
An Introduction to Coordination Compounds .25
11. For Co in oxidation state II, predict the overall charges of the coordination complexes shown in the

reactions below:
OH OH2 CI
HO Ot2 NaOH
HO M OH2 + 6H20
CO

HO H2O OH2 C C
OH OH2 OH2
(a) z = +2, x = -2, y= +2 (b)z =0, r= +2 y= -2
(c) z =0, x = +2 y = +2 (d) z = -2, x = +2, y=-2

12. What is the change in oxidation state of cobalt in the following reaction ?

[Co(NH)4Cl2] +H20 [Co(NH3 )4 (H20)CI]f* +CI

(a) increases from +2 to +3 (6) decreases from +3 to +2

(c) increases from +1 to +2 (d) does not change

13. What is the oxidation state ofiron in Na2[Fe{CO)4]?
(a)-2 (b)-1
(c) 0 (d) 2
14. In the complexes[Fe(CN)6]*and[Co(en)3]°*, the coordination numbers ofiron and cobalt are,
respectively (en =
ethylenediamine):
(b) 12 and6
(a) 6 and 6
(c) 6 and 3 (d) 3 and 3
15. Chelate effect is
(a) predominantly due to enthalpy change
(b) predominantly due to entropy change
(c) independent of ring size
and enthalpy change
(d) due to equal contribution of entropy
16. Given the molecular formula ofthe hexa-coordinated complexes

) CoCl3 (NH3)6
(I)CoCl3(NH3)s
(ILI)CoCl3 (NH3)4
molecules in (I), (11) and (II) respetively are 6, 5 and 4 then the
Ifthe number of coordinated NH3
oxidation state of Co in (), (1I) and (lU) are respectively:
+4 (b) +3, +2, +1
(a) +6, +5,
(d) +3, +3, +3
(c) 0, +1, +2

ANSWERS

3. (c) 4. (a) 5. (d) 6. (c) 7. (a)

1. (d) 2. (b)
10. (a) 11. (b) 12. d 13. (a) 14. (a)
8. (a) 9. (c)
15. (b) 16. (d)
 126} Coordination Chemistry

Suojoctive Qnestions
1. How many chelate rings are present in the following complexes?
(a)[Ca(EDTA)J (b)[Co(en)3]**
()[Co(dien)2* (d) [Cd(trien)]*
(e) [K(18- crown -6]
2. What is the expected freezing point depression of0.01 m [Co(NH3)6 ]Cl3 complex ?

(K =-186° C/m)
3. Arrange the following complexes in the increasing order of:
(a) conductivity in aqueous solution.
(b) depression in freezing point considering 0.1 m concentration of each complex.
[Co(NH3)4Cl2]Cl, [Co(NH3)5 CI]cl2, [Co(NH3)6Cl3
4. A (2+, 1) electrolyte complex is expected to have higher molar conductivity than (1+, 1)
electrolyte complex. Explain.
5. A solution is made by dissolving 0.875 g of Co(NH3 )4 Cl3 in 25.0 g of water which freezes at
-0.56°C. Suggest the structure of this compound. Calculate number of moles of ions produced
when one mole of Co(NH3)4Cl3 is dissolved in water.
6. Define the following
terms
(a) Coordination compounds (b) Ligands
(c) Ambidentate ligands (d) Chelating ligands
(e) Flexidentate ligands (f) Bridging ligands
(g) Donor atom (h) Macrocyclic ligands
(i) Coordination number G) Counter ion
(k) Complex ion.
7. What is the coordination number of the metal in each of the following compounds ?
(a) [Co(en)31**
b)[Co(gly)3]
(c)[ZrF1
(d) [Ce(NO3)61
(e) Na2[Fe(CN)5 (NO)]1
( [Ca(edta)]
(g) [Ni(Hdmg)2 ]

O00
Structure and Isomerism in Coordination
-
Compounds 2.41
. Exercise

FiCl in the Blanks

1. The N0 ligand can form. . . 1Somers.

2. Thecomplex cis-[Co(en) 2 (NH3 )CI]4T can exist as ***********

.

3. The complex [Co(NH3)4Cl2]

can exist . . 1SOmers.

4. The complex [Co(NH3)4Cl(NO2 )]Br can exist as structural isomers as and

isomers.
5. The complex [Co(EDTA)] is a .
6. cis-4Co(en)2 Cl2]' is optically . ******

7. Chirality is the essential condition for. .****

8. The complex [Co(NH3 )3 (NO2)3] show two geometrical isomers namely and
**

Ans. 1. linkage 2. enantiomers

3. geometrical 4. linkage, ionization
5. chelate 6. active
7. optical activity 8. facial, meridonal ]

O6joctive Quostions
1. Number of stereoisomers ofthe compound [Co(NH3)3 Cl2Br]are: .
(a) 1 (b) 2
(c) 3 (d) 4
2. The complexes [Co(1,2-diaminopropane), Cl2l" and [Co (1,3-diaminopropane), Cl2l represent
an example of:
(a) ligand isomerism (b) linkage isomerism
c) ionization isomerism (d) coordination isomerism
3. The number of possible isomers for the octabedral complex ion [Co(en)Cl2Br2 ] is:
(a) 2 (b)4
c) 6 8
4. Fora complex, MX 3Y3 possessing trigonal prismatic geometry, the number ofpossibBle isomers is:
(a) 2 (b) 4
(c) 3 (d) 6
5. The number of possible geometrical isomers for octahedral Co(ox) (PMe 3 )2 NH3Cl is:
(a) 2 (b)3
(c) 4 (d) 5
 Coordination Chemistry
6. The existence of two different coloured complexes of Co(NH3 )4 Cl2 is due to

(a) optical isomerism (b) linkage isomerism

c) geometrical isomerism (d) coordination isomerism
7. The isomerisms that are possible in the Co(III) complexes [Co(NH3)3 (NO2)3] and
[Co(NH3)5 NO2 Cl2, respectively, are:
(a) coordination and position (b) optical and linkage
(c) geometrical and linkage (d) optical and optical
8. The complexes [Co([NH3)4 (H20)CI] Br and [Co(NH3)4 Br2 ]CI. H20 are examples of
(a) ionization isomerism (6) linkage isomerism
c) geometrical isomerism (d) optical isomerism
9. The pair of ions that most commonly forms complexes with coordination number 2 is
(a) Cd (1) and Hg(II) (b) Cu (I) and Hg ()
(c) Cd (1) and Hg () (d) Cu (1) Hg (1)
10. The octahedral complex/complex ion which shows both facial and meridional isomers is:
1) triglycinatocobalt(1II) (6) tris (ethylenediamine cobalt(11))
(c) dichlorodigylcinatocobalt(11) (d) trioxalatocobaltate(1I)
11, Which one
ofthe following compounds has optical isomers ?
(a) trans-[Co(en)2 Cl;]" (en= ethylenediamine)
(b) [PICl2(NH3)2]
c)[Co(en) 1*
(d[Fe(n -CsHs)2]
12. The complex [PtCI{NCS)(NH3 )21is capable ofexhibiting:
(a) ionization isomerism (b) linkage isomerism
(c) coordination isomerism (d) optical isomerism
13. The complexes [Cu(NH3)41 (PMCl4 Jand [Pt(NH3 )4]{CuCI4 Jare an example of:
(a) ionization isomerism (b) linkage isomerism
(c) coordination isomerism (d) geometric isomeric
14. A complex of Ni(II), E[NiCl (PPh3 )2] is paramagnetic. The analogous Pa(l) complex is
diamagnetic. The numberofisomers that will exist for the nickel and the palladium complexes are:
(a) one, one b) one, twwo
(c) two, one (d) two, two
15. The number of isomers that exists for [Mo(C;H5N)3 (CO); ] is:
a) one b) two
(c) three d) four
16. The complex[Co(NH3)5 (NO2)" is capable of exhibiting
(a) optical isomerism (6) geometrical isomerism
(c) ionization isomerism (d) linkage isomerism
Structure and Isomerism in Coordination Compounds 3,

17. The complex that exists as a pair of enantiomers is:

(a) trans-[Co(H2 NCH2CH2NH2 )2Cl21
(b) cis-[Co(NH3 )4Cl21*
(c) [Pt(PPh3)CI)(Br)(CH3)
(d) [Co(H2NCH2CH2NH2 )s 1*
18. The number of possible isomers for [Ru(bpy)2 C2 ] is (bpy = 2, 2-bipyridine)

(a) 2 3
(c) 4 (d) 5
19. The number of possible isomers for the square planar mononuclear complex [(NH3)2 M(CN)2 ]of
a metal M is:
(a) 2 (b) 4
(c) 6 (d) 3
and the
20. Green coloured Ni(PPh2Et)2 Br2, has a magnetic moment of 3.20 B.M. The geometry
number ofisomers possible for the complex respectively, are
(a) square planar and one (b) tatrahedral and one
(c) square planar and two (d) tetrahedral and two
21. The total number of stereoisomers of[CoCl3 (NO2)31* ion are

(a) 2 b) 3
(c) 4 (d) 6
22. Among the following complexes:
) [Ru(bipyridyl)3 1*
i) [Cr(EDTA)]
(11) trans-[CrCl2 (oxalate)2]
(iv) cis-[CrCl2 (oxalatate)2]°
thechiral complexes are
(a) (i), (i), (iv) (b) (i), (ii), (iv)
c) (i), (ii), (ii) (d) i), (in), (Gv)
23 he number of stereoisomers of trans-CoCl2 {triethylenetetramine)]Br is
a) One b) Two

c) Three (d) Four

ANSIUERS
1. (d) 2. (a) 3. b) 4. (b) 5. (c) 6. (c) 7. (c)
10. (a) 11. (c) 12. (b) 13. (c) 14. (b)
8. (a) 9. (d) 21. (a)
16. (d) 17. (d) 18. (b) 19. (c) 20. (b)
15. (b)
22. (a) 23. (c)
IUPAC Nomenclature of Coordination Compounds
3.17

Exercise

FieeintAeBlanks
1. Oxidation state ofPt in complex cation and complex anion in[Pt(NH3)4Cl2][PtCl4 ]is.
and...... respectively.
4+
NH2 and it is a
2. Oxidation state of cobalt in (H3N)4CoK Co(NH3)4 is

. . . Complex.

3. In [Co(gly)2 (NH3 )CI]. i . . is abidentate ligand and gly is the abbreviation for..
14+
NH2
the prefix ju-is used for the ligands are
4. In the complex (H3N)4 Co Co(NH3)4 ,

02
. alld
5. The IUPAC name of the complex facfCo(CH3 NH2)3Cl3 ]is..
6. The IUPAC name of the complex [Be^O(CH3COo)%] i s . . .
7. Ni (aq.) reacts with alcoholic solution of dimethylglyoxime in alkaline medium, a red colour

complex is formed. The IUPAC name of this product is ...

8. The complex [Co(NH3 ); (NO2)3] show two geometrical isomers namely and

* * * * * * * *

[Ans. 1. +4, +2 2. +3, bridged

3. gly, glycinato 4. NH2,02
5. fac-trichlorotris(methylamine)cobalt(III)
6. hexakisq-acetato4u-oxido tetraberylium(I)
7. bis(dimethylglyoximato)nickel(1I) 8. facial, meridional ]

O6jactive Questions
1. The IUPAC name of cis{Co(en)2 Cl2]" is:
(a) bis(ethylenediamine)dichloridocobalte(11) (b) dichloridobis(ethylenediamine)cobalt(111)
)cis-dichloridobis(ethylenediamine)cobalt([|i1)
(d) cis-dichloridodi(ethylenediamine)cobalt(II)
2. The IUPAC name oftrans{Cr(NCS)4(NH3 )2] is:
(a) trans-diaminetetrathiocyanato-k N chromate()
() trans-diamminetetrathiocyanato-kN chromate(III)
(c) rans-tetrathiocyanato-kN diamminechromium(III)
(d) trans-diamminetetrathiocyanato-kN chromium(III)
 Coordination Chemistry
3.18
3. Oxidation number of Os in [NOs(PPh 3 )Cl3 (NEt2)] is:
(a) +2 (b) +3
(c) +5 (d) +6
4. The TUPAC name ofmer{Co(NO2)3 (dien)] is:
(a) mer-ethylenediaminetrinitrocobalt(I) b)mer-diethylenetriaminetrinitrito-kNcobalt(I)
(c)mer-diethylenediaminetrinitrocobalt(11) (d) mer-trinitrodiethylenetriaminecobalt(|1)
5. The IUPAC name of Na 3 [Fe(CN) 5 NO] is:
(a) sodium pentacyanidonitrosyl iron(11) (b) sodium pentacyanidonitrosonium ferrate(D
(c) sodium nitrosoniumpentacyanido ferrate() (d) sodium nitrosylpentacyanido ferrate(1)
6. Which one of the following is a correct representation of tetraammine nickel(I) hexacyanido
ferrate (III) ?
(a) [Ni(NH3)4 ][Fe(CN)6] (b)[Ni(NH3)4 ]3 [Fe(CN)6 l4
(c) [Ni(NH3)4 ][Fe(CN)6l2 d) [Ni(NH3)4 l3 [Fe(CN)6 l2
7. The IUPAC nomenclature
of Na[PCI]is:
(a) sodium hexachloridophosphine(V) (b) sodium hexachloridophosphate(V)
(c) sodium hexachloridophosphine (d) sodium hexachloridophosphite(V)

ANSWERS
1. (c) 2. (b) 3. (d) 4. (b) 5. (b) 6. (d) . (b)

Suojective Auostions
1. Write the IUPAC name ofthe following complexes
(a)[Pt(py)4][PtCl4] (b)[Cr(NH3)6][CoF6 ]
(c)[Cr(en)3][Ni(CN)s] (d) [Co(NH3)5ONO]
(e)[Cr(NH3)sCO3]Cl ) [Ni(NH3)2 (H20)NO2 )]Br
2 Write the formula of following complexes:
(a) Pentaammine chromium(I1I)-44-hydroxidopentaammine chromium(I) chloride
b) Diammine diaqua dicyanido cobalt(II) chloride
(c) Pentaammine thiocyanato-xN chromium(1) tetrachloridozincate(1I)
(d) Sodium dithiosulphatoargentate()
(e) Tetraammine carbonato cobalt(1II) chloride
(1) Potassium tetrafluoridoargentate(1)
3. (a) Give the IUPAC name ofthe following:
)[Pt(CGHsN)(NH3 )(NH2OH)(NO2)* i) [(NH3 )Co-02-Co(NH3) 1(NO3)4
(ii) Li[Ni(PF3)3l3] (iv) [Ag(NH3)2 ]2 [PtCl6]
(b) Write the formulae ofthe following:
() Tetramethylammoniumtetrachloridooxidovanadate(IV)
(ii) Potassium carbonylpentacyanido(C)cobalt(III)
ii) Tris(thiourea)bismuth(11) nitrate
 Coordination Chemistry

Exercisse

Fiee in the Blanks

1. In CrF2,Cr() is octahedrally surrounded by six F ligands with two longer Cr-F bonds and four
shorter ones because of . . . .
2. The [FeX 61*, where X is a monodentate ligand, has one unpaired electron. The X ligand
produces a... .field.
3. CN is a o-donor as well as . . . igand.
4. NH3 is a... .. donor ligand.
5. The dipositive 3d-transition metals which lie on the line of hydration energy curve are .
6. [Fe(NH3)61 is unstable because NH3 does not form. with Fe2+
7 The algebraic sum of all energy shifts of all orbitals should be .
8 The d-orbitals which participate in dsp'-hybridization are. ******* ... ana . . . . . . .

9. The d-orbitals which participate in sd -hybridization are. *******.

10. The orbitals with highest energy in z-out and z-in distorted octahedral complexes are . **

and... . . . . . respectively.
11. The highest energy orbital in trigonal bipyramidal complex is °°*°**°*
12. The hybridization in [Cu(NH3 )414 is..
13. According to CFT, the bond between metal cation and the ligands is ..
14. Among the [Co(NH3)61*.Ir(NH3)61*. [Fe(bpy)3]*" the A, is highest for ...
15. CN ligand causes strong splitting of d-orbitals in complexes because it is a good.
16. CI ligand causes weak splitting of d-orbitals in complexes because it is a good.
17. The geometry of [NiCl41* and [PtCl4]* are. and.. respectively.
[Ans. 1. Jahn-Teller distortion 2. strong
3. T-acceptor 4. O
5. Mn4T and Zn* 6. t -bond
7. zero 8. d d2
9. dry dyz, dz 10. d 2 "2
11. d2 12. spd
13. ionic 14. [Ir(NH3)613*
15. T-acceptor 16. T-donor
17. tetrahedral, square planar ]
Theories for Metal-Ligand Bonding in Complexes 457

O6joctive Questions
1. The crystal field stabilization energy (CFSE), in units ofA, for [CoF; (H,0)3 ]is:
(a) 0 (b) 0.4
(c) 0.8 (d) 1.8
2. For Ti(H20),", the absorption maximum due to d-dtransition is found at 20,000 cm.Therefore,
the crystal field stabilization energy is:
(a) 20,000 cm (b)x20,000cm
(c) 8,000cm (d)-8,000cm
3. Which one ofthe following octahedral complexes will be distorted?
(a) [Cr(H20),12* (b) [Cr(H20)61*
(c) [Mn(H20),12* (d) [Fe(H20)%1*
4. The crystal field splitting energy (A) for CoCl is 18000cm. The A for CoCI would be

(a)18000cm (b)16000cm
(c) 8000cm (d)2000cm
5. The crystal field stabilization energy (CFSE) will be the highest for:
(a) CoF (b) Co(CNS)
() Mn(H20) (d)Co(NH3)"
6. Among (CH3)3 P, NO,CN and I ligands, the one which is not a t-acceptor ligand is:
(a) l5 (b) CN
(c) NO+ (d) (CH3)3P
7. The complex with maximum CFSE is

(a)[CoCl4 b)[Co(H0),1*
[CoF3 (H0)3 d)[CoF61
8. The compound which exhibits Jahn-Teller distortion is
(a) [Mn(H20)612+ (b) [Mn(H20)%1**
(c)[C(H,O),* (d) [Fe(CN)61
9. The number ofmaganese ions in tetrahedral and octahedral sites, respectively in Mn304 are

(a) one Mn and two Mn3* b) one Mn" and two Mn

(c) two Mn" and one Mn (d) two Mn2+ and one Mn
10. The spinels CoFe204 and FeFe204, respectively are:
(b) inverse and normal
(a) inverse and inverse
(c) normal and normal (d) normal and inverse
 4.58 Coordination Chemistry
I . In the trigonal bipyramidal crystal field, the d-orbital with the highest energy is :

(a) dy b) d
(C) dyx (d) d
12. The magnetic moment ofthe complex K3 [CoF6 lis 5.0 B. The total stabilization energy will be :
(a) -0.4A (b)-0.4A, +P
(c)-2.4A +3P (d)-1.8A, +3P
13. For the complex ion |Cu(NH )o]2*, the coordination geometric will be :
(a) octahedral (b) tetragonally distorted octahedral
) trigonal prismatic (d) trigonal antiprismatic
14. The complex ion [Ni(CN)4] has square planar configuartion with magnetic moment of zero.
What would be the magnetic moment if it were tetrahedral?
(a) 4.84 B.M. (b) 1.73 B.M.
() 2.87 B.M. (d) 5.9 B.M.
15. Arange the following metal complex in order oftheir increasing hydration energy
[Mn(H0)612+ [VH;0)%1* [NiH20)%* Ti(H20)1+
(P) (Q) (R) (S)
(a) S <P<Q<R (6) P<Q<R<S
(c) Q <P <R<S (d) S<R<Q<P
16. The structure of the complexes [Cu(NH3 )4]CIO4)2 and [Cu(NH3)4 ]CI0,) in solution
respectively are:
(a) square planar and tetrahedral
(b) octahedral and square pyramidal
(c) octahedral and trigonal bipyramidal
(d) tetrahedral and square planar
17. The corect statement about the Cu-N bond distance in [Cu(NH3)612* is :
(a) all the bond distance are equal
(b) the axial bonds are longer than the equatorial ones
(c) the equatorial bonds are longer than the axial ones
(d) all the bond distance are unequal
18. The symmetry required for the ligand group orbitals (LGO) for the n-base ligands to have
T-interactions with the metal d-orbitals in an octahedral geometry is
(a) alg (b) b2g
()eg (d) t2g
19 Hybridization of Ni(I) in K2[NiBra ]is:
(a) dsp (b) sp3
(c)spd (d) ds
20. The CFSE for the following d' metal ions (V".Cr", Mo**) decreases in the following order
Theories for Meta-Ligand Bonding in Complexes 4.59
(a) v>Cr > Mo3 b)Cr v2 >Mo
(c) Mo">Cr3* >y2+ (d)Cr3> Mo3> y2+
21. Which one ofthe following complexes is Jahn-Teller distorted?
(a) Co(NH3 6 (b) Cr(H0)
(c) Cu(H20); (d) [Fe(CN)61
22. Which ofthe following shows NORMAL spinel structure?
(a) Fe304 (b) Mn 304
(c) NiAl20O4 (d) La2Cu04
23. On molecular orbital treatment of [Mn(CO)6l', the symmetry of the LGO that is NOT

sigma-bonding,is:
(a) A1g (b) Tig
(C)1u (d) Eg
24. CFSE of transition metal complexes can be detemined by :
(a) UV-visible spectroscopy (b) IR spectroscopy
(c) Microwave spectroscopy (d) NMR spectroscopy
25. Which one ofthe following pairs of electronic configuration of high-spin transition metal ions (3d)
in an octahedral field undergo a substantial Jahn-Teller distortion?
(a) d5,d (b)d,d
(c) d,d* (d) d,d
26. Jahn-Teller distortion of CuSO45H20 acts to:
(a) raise symmetry
(b) remove an electronic degeneracy
(c) cause loss of H20 ligand
(d) promote a d-electron to an antibonding molecular orbital
27. According to crystal field theory, Ni4" can have two unpaired electron in:
(a) octahedral geometry only (b) square-planar geometry only
(c) tetrahedral geometry only (d) both octahedral and tetrahedral geometry
28. Forthe complexes
(A) [Ni(H20)%1* (B) [Mn(H,0)6]2* (C)[Cr(H20)%1+ (D) [Ti(H20)61*. the ideal
octahedral geometry will not be observed in
(a) (A) and (D) (b) (C) and (D)
(c) (B) only d) (D) only
29. The enthalpies of hydration of Ca", Mn and Zn4" follow the order
(a) Mn2 > Ca2 >Zn2+
(b) Zn>Ca > Mn4*
(c) Mn2> Zn2 > Ca2*
(d)Zn> Mn>Ca
 4.60 Coordination Chemistry
30. The correct order of acidity among the following species is
(a) [Na(H20)sl >[Ni(H20)%1*" > [Mn(H20)%1*" > [Se[H,0)%1P*
(b) [Sc(H20)%* > [Ni(H20),1* > [Mn(H,O)61* > [Na(H20)%I*
()[MngH20)%* > [Ni(H,0)61* > [Sc(H20),1* > [Na(H,0)61*
0)scH206* >[Na(H,0)%1r >[Ni(H20)«1P* >[MntH,0)61*
31. The correct order of d-orbital splitting in a trigonal bipyramidal geometry is:
() da >d >da2.dy (b) d dy dz2,dy >
() d22,dy >d2 > dn,dyz (d) d>dp, dy da dy >

32. As a ligand Cl is
(a) only a o-donor b) only a T-donor
(c) both a g-donor and a t-donor (d) ao-donor and a o-acceptor
33. Which of the following complexes has the highest number of unpaired electrons?
(a) [FeCl4I (b)[Vo(H20)51*
(c) HgICo(NCS)4] (d) [Co(NH3)61*
34. Which is the correct statement about the Ni-N bond in
[Ni(NH3)6]*?
'a) All are of equal bond lengths
(b) The two axial bonds are longer than the four equatorial bonds
(c) The four equatorial bonds are longer than the two axial bonds
(d) None of the bond length are equal
35. The observation of equal Cu-O distances in the hexa-coordinated
Cu(II) complex,
K2Pb[Cu(NO2)6] is best understood in terms o
(a) Failure of the Jahn-Teller theorem to predict the structure of this complex
(b) Error in the crystallographic estimate of Cu-O distances
() Dynamic Jahn-Teller distortion of the Cu-O bonds
(d) Symmetrical distribution of the nine valence electrons of Cu(I)
36. It is known thatpK, of water is 15.7. Based on this water pK, benchmark, arrange the following
solvated metals-aqua ions in order of their increasing acidity
Mn2(H,0)6, Fest (H20)6. Cu" (H20)6. Ca (H20)8.
(a) All have same acidities

(b)Fe<Cu" <Mn"<Ca
(c) Ca" <Cu2 < Mn2* <Fe3+
(d)Ca2 Mn2 <Cu2 < Fe3*
37. The pair of simple and inverse spinels respectively isS
(a) Fe304 and Mn 304 (b) Fe304 and Co304
(c) Mn304 and NiFe204 (d) NiFe204 and Co304
Theories for Metal-Ligand Bonding in Complexes
38. Stabilisation of highest oxidation states of transition metals by strong electronegative ligands due
to
(a) dn(L)
dt(M) bonding (b) pm(L) dr(M) bonding
(c) dr(M)> pr(L) bonding (d) dn(M)> dr (L) bonding
39. Which pair has zero CFSE?
(a) Ca, Mn, Zn*2 b)Ca, Mn, Zn*
(c) Ca*2, cu2, Zn *2 (d) Ca2, Fe*3, Zn*2
40. The increasing order of crystal field splitting (A,) is
(a) C5H5N <en < N02 < Phen (b)en<CsHsN < Phen < NO

(c)en< NO2 <C5H5N < Phen (d)C5HsN < NOZ <en < Phen
41. In the solid state, the CuClion has two types of bonds. These are:

(a) three long and two short 6) two long and three short
(C) one long and four short (d) four long and one short
42. Identify the order representing increasing n - acidity of the following ligands
C2F4, NEt3, CO and C2H4
(a)CO<C2F4 <C2H4 <NEt 3 (b)CF <C2H4 < NEt3 <CO
(c) C2H4 < NEt3 <CO< C2F4 (d) NEt3 <C2H4 <C2F4 <CO
43. The correct spinel structure ofCo304 is
(a)(Co (2Co*),04 (b) (Co) (2Co*Co*).04
(c)(CoCo*), (Co*"),04 (d)(2Co"), (Co*),04
44. Amongst the following, the complex ion that would show strong Jahn-Teller distortion is
(a) [Cr(H0)61* (b)[Ti(H20)%*
(c)[Co(H20)%12+ (d)[Fe(H20)%12*
45. MnCr204 is:
(a) normal spinel with total CFSE of-15.5 Dq
(6) inverse spinel with total CFSE of-15.5 Dq
(c) normal spinel with total CFSE of -24 Dq
(d) inverse spinel with total CFSE of -24 Dq
46. MnCr204 is likely to have a normal spinel structure because:

(a) Mn" will have a LFSE in the octahedral site whereas the Cr will not
(b) Mn is in +2 oxidation state and both the Cr are in +3 oxidation state
(c) Mn is in +3 oxidation state and 1 Cr is in +2 and the other is in +3 state
(d) Cr" will have a LFSE in the octahedral site whereas the 2+ ion will not

47. Compounds K2 Ba[Cu(NO2)6] (4) and Cs2Ba[Cu(NO2 )%1(B) exhibit tetragonal elongation and
tetragonal compression, respectively. The unpaired electron in A and B are found respectively, in
orbitals
 4.62 Coordination Chemistry

(a) d2 and (b) d2,2 and d,2

d2_2
(c) d2 and
d2 (d) d22 and
d2
48. Given that the crystal field stabilization energy for [Co(H20)%1*" is 7360 cm", the calculated
value of A in kJ mol is
(a) 87.93 (b) 73.28 (c) 6133.33 (d) 102.42
49. The oxidizing power of[CrO41 [Mn041 and [Fe0] follows order
(a) [CrO1 <
[MnO4] <[Fe041 (b)[Fe041 <[MnO41* <[CrO]
()[MnO04 <[Fe041 <[CO41* (d)[CrO1 <[Fe04]* <[Mn04*
50. The correct statement for Mn-O bond lengths in [Mn(H20))%1* is:
(a) all bonds are equal
(b) four bonds are longer than two others
(c) two bonds are longer than four others
(d) they are shorter than the Mn-O bond in[Mn04]
51. The acidity of molecules is usually measured by a parameter called the pka . Metal ions (M"*)
solubilized in water form solvated aqua complexes commonly denoted by [M(H,0)m ]* or
Mag. It is known that the pka of coordinated water in such metal-aqua complexes will be
different from that of bulk water. For the following set of metal-aqua complexes
Caaq, Feaq. Mna. Feaq arrange the complexes with decreasing value ofexpected pK ofthe
coordinated water molecule:
2+ > 3+
(a) Fe2a, > Mnaa. > Caa, > Fe 24 (b) Caad, > Mnaq, > Fe aa. Fe aq4
(c) Fea> Feaq, > Mnaq >Caag (d) Mna4 > Ca,> Fea, > Feaa
52. IfAo is the octahedral splitting energy and P is the electron pairing energy, then the crystal-field
stabilization energy (CFSE) of[Co(NH3 )614* is:
(a)-0.8 A0 +2 P b)-0.8 Ao +1P (c)-0.8AAg (d) -1.8 Ao +3 P
53. The spinel structure of MgAl204 has cubic close packed arrangement of oxide ions. The fractions
ofthe octahedral and tetrahedral sites occupied by cations, respectively, are
(a) 1/8 and 1/2 (b) 1/4 and 1/2 (c) 1/2 and 1/4 (d) 1/2 and 1/8
54. In trigonal prismatic ligand field, the most stabilized d orbital is :
(a) d? (b) dy (c) dye (d) dyz
55. The geometry around Cu and its spin state for K3CuF6 and KCul 2

[HL H2NCONHCONH2], respectively are:

(a) (octahedral, high-spin) and (square planar, low-spin)
(b) (octahedral, low-spin) and (square planar, low-spin)
(c) (trigonal prismatic, high-spin) and (tetrahedral, high-spin)
(d) (trigonal prismatic, low-spin) and (tetrahedral, high-spin)
Theories for Metal-Ligand Bonding in Complexes 4.63
56. Identify the high-spin complex amongst the choices given below
(a) [Co(NH3)61* (b) [Co(CN3)6]-
(c)[CoF (d) None of the above

FINSIUERS
1. (b) 2. (d) 3. (a) 4. (c) 5. (d) 6. (a) 7. (b)
8. (b) 9. (a) 10. (a) 11. (d) 12. (a) 13. (6) 14. (c)
15. (a) 16. (a) 17. (b) 18. (d) 19. (b) 20. (c) 21. (c)
22. 23. (b) 24. (a) 25. (b) 26. (b) 27. (d) 28. (d)
29. (d) 30. (b) 31. (d) 32. (c) 33. (a) 34. (a) 35. (c)
36. (d) 37. (c) 38. (b) 39. (a) 40. (b) 41. (a) 42. (d)
43. (a) 44. (a) 45. (c) 46. (d) 47. (b) 48. (b) 49. (a)
50. (a) 51. (6) 52. (c) 53. (d) 54. (6) 55. (a) 56. (c)

Suojective Questions
1. Pt ion forms octahedral whereas Pt4 forms square planar complexes. Explain.
2. P(1) makes square planar complexes almost exclusively. Explain with the help of crystal field
theory.
3. What is the effect of T-donor and T-acceptor ligands on A,? Explain on the basis of ligand field

theory.
4. Crystal field splitting energy A, for [Cr(NH3)6]4* is 10,200 cm while for [Cr(NH3)41* is

5,900cm Explain.
5. Draw the crystal field splitting diagram for [CoCl41 and calculate CFSE.
6. Determine the CFSE of a d -complex having 10 Dq= 25,000 cm and P = 15,000cm (mean

pairing energy).
7. Which complex in each of the following pairs will have greater crystal field splitting and why?
(a) [Co(en)3]** or [Rh(en)3]** (b) [Cr(CN)61 or [Cr(NH3)61**
(c)[Fe(CN)6J* or [Ru(CN)61* (d) [Fe(H20)%1** or [Fe(CN)%1
(e) [Co(NO2)61* or[Co(ONO)%J*=
8. Tetrahedral complexes are high spin. Explain.
9. Explain the variation of lattice energies of the divalent 3d-series transition metal halides.
10. K2[NiF6] is diamagnetic while K3[CoF%] is paramagnetic. Both have same d-configuration.

Explain on the basis of CFT.

11. For a complex ion [MnL 6 ] , where L is a neutral mono-dentate ligand, the mean pairing energy

(P) is found to be 28,000cm.Ifthe magnitude of A, is 21,000 cm, calculate CFSE.

value of only 3.2
12. K4[Cr(NCS)6] has a magnetic moment of 5.0 B.M while K4[Cr(CN)6 1] has a

B.M. Give the geometry of each complex on the basis of VBT.

 Coordination Chemistry

13. Define Jahn-Tellertheorem. Giving reason, explain in which case this effect would be observed?

or
14. On the basis of VBT, account for the magnetic properties of:
[Ni(NH3 )s1* Gi) Co(NH3)612* (ii) [Fe(CN) 1 (iv)[Cr{(CN)6I ()[Co(NH3 )613*.
15. In the crystal ofCuF2,Cu2ion is surrounded by six F with four F at a distance of 193 pm while
two F 227 pm.
at Explain.
16. For tetrahedral complexes, A, =A. Explain.
17.
The
VBT,
magnetic moment of[MnBr 1 and [Mn(CN)6 are 5.9 and 2.9 B.M. respectively. Using
assign the
geometries of these complexes.
18. Cobaltqiis easily oxidizedtocobalt(1) inthe presence ofstrongfield liands but the isoelectronic
nickel(III) complexes are oxidizing agent. Explain on the basis of CFT.
19. Solid CrFg cotains a Cr() ion surounded by six F" ions in an octahedral geometry, all the Cr-F
distances are 190pm. However, MnF3 is in a tetragonal distorted geometry with Mn-F distanes of
179, 191 and 209 pm (two of each). Explain.
20. F is a weak ligand whereas CN is a strong. Explain on the basis of LFT.
21. 4d and 5d-series trastion elements form low spin
complexes. Explain.
22. The enthalpy of hydration of Cr4t is 460 kcal mol, In the presence of CFSE, the value of AH
would be 435 kcal mol. Estimate the value of A, for [Cr(H20)6 ]**
23. The magnetic moment of[Fe(H20)%]°" was found to be 5.9 B.M. and of[Fe(CN)6] is 1.9 B.M.
Account for the above observation on the basis of VBT.
24. The [Ni(CN)41 ion is square planar and diamagnetic whereas [NiCl4] is tetrahedral and
paramagnetic. Explain.
25. Which is more labile in aqueous solution, Cr " or Mn*? Explain.
stable and which one is more

26. Weak ligands form high spin complexes whereas strong ligands form low spin complexes with
3d-transion metal ions. Explain.
27. Square planar geometry is especially common for d'-configuration. Explain.
28. (i) Define Jahn-Teller theorem.
(ii) Hexacoordinated structures are found to possess distorted octahedral structures due to
Jahn-Teller distortions. Rank the following compounds in terms of degree of deviation from
regular octahedral structure.
(ni) Explain your reasoning with the help ofcrystal field spliting diagram:
Cr(CN)1. [CuH;0)%1 and [Cr(OH; )%1**

O00