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Sol_1 18e- Rule Applications & 16e-Rule
HINTS & SOLUTION
1. Since, (C6H6)M(C4H4) obey 18 e– – rule
 (C6H6)M(C4H4) = 18
6 + M + 4 = 18
M + 10 = 18
M = 18 – 10
M 8
Since, ‘Os’ has electron count 8.
Correct option is (a)
2. Let us consider that the complex obey
18 e– – rule,
 TcBr(CO)n = 18
7 + 1 + n × 2 = 18
8 + 2n = 18
2n = 18 – 8
2n = 10
n5
 The complex will become TcBr (CO)5.
3. Since [Os(CO)3(CH3)2]n obey 18 e– – rule
 TEC will be, 8 + 3 × 2 + 2 × 1 + n = 18
8 + 6 + 2 + n = 18
n = 18 – 16
n2
And we know, the charge obtained will be of opposite sign of the value calculated.
 Correct option is (a)
4. TEC of (5 – C5H5)Re(6 – C6H6)
= 5 + 7 + 6 = 18 e–
5. TEC of PtCl2en = 10 + 2 + 4 = 16 e–
6. Since we know, the number of ligand atoms attached to the metal atom is called hapticity.
The hapticity for C6H6 are 2, 4, 6
Now, if [(x – C6H6)Ru(y – C6H6)] obeying 18 e– – rule we have

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QUANTA POINT Sol-(1) /18e- Rule Applications & 16e-Rule
TEC = x + 8 + y = 18
x + y = 10
which means x = 4 and y = 6
7. [Mn(CO)5Cl] = x + 0 + (–1) = 0
x=1
 Mn+1 have 6d- electron count.
8. TEC of Cp2ZrCl2 will be
=5×2+4+2
= 10 + 4 + 2
= 16 e–
9. [M (CO)X]Z–
[V (CO)6]–
5 + 12 + 1 = 18e
Option (b) is correct.
10. Since Cr(3 – C5H5) (CO)n(CH3) obeys 18 e– – rule
 TEC will be, 6 + 3 + 2 × n + 1 = 18
10 + 2n = 18
2n = 8
n=4
 The complex become, Cr(3 – C5H5) (CO)4(CH3)
11. Since, the given complex obeys 18 e– – rule.
 5 × 2 + M + 2 = 18
12 + M = 18
M=6
 Option ‘b’ is the right answer as ‘W’ has 6 e– – count.
12. TEC of (5 – C5H5)2Co = 5 × 2 + 9
= 10 + 9
= 19 e–
(5 – C5H5)2Co  (5 – C5H5)2Co+ + e–
Also act as reducing agent.
13. Since M(CO)2(CS)(PPh3)(Br) followes 18 e– – rule
 M + 2 × 2 + 2 + 2 + 1 = 18
M + 4 + 5 = 18
M = 18 – 9
M=9
 Co is the answer as it show e– – count 9.
14. Value of X  2 (Cp) + Mo + x (H) – 1 = 18
10 + 6 + x (H) – 1 = 18
15 + x (H) = 18e

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QUANTA POINT Sol-(1) /18e- Rule Applications & 16e-Rule
x (H) = 18 – 15
x = 3e
Oxidation state  2 (Cp) + Mo + 3 (H) = 1
– 2 + Mo – 3 = 1
Mo – 5 = 1
Mo = 1 + 5
=+6
Correct option is (a)

15. TEC of option ‘a’ is—

=8+1+2+2+2+1+2
= 18e–
16. Since the complex follows 18e––rule
 TEC = 9 + 2 + 2 × n + 2 × 2 + 1 = 18
 16 + 2n = 18
2n = 18 – 16
2n = 2
n=1
 Complex become IrBr2(CO)(PPh3)2(CH3)
17. [CpMo(CO)3]–
Oxidation state = –1 + x + 0 = –1
x = –1 + 1
x=0
 it has 6 electron count according to converted d system.
18. Since the complex follows 18e––rule
 TEC of [Ru(CO)4GeMe3]x will be
 8 + 4 × 2 + 1 + x = 18
 8 + 8 + 1 + x = 18
17 + x = 18
x = 18 – 17
x=1
As the charge calculated is +1  the answer will be of opposite charge i.e. –1.
19. Oxidation state of [CpCo(CO)2]2(µ – CO)
 –1 × 2 + 2x + 0 = 0
2x – 2 = 0
2x = 2
x=1
 d-electron count will be 9 – 1 = 8e–.
20. Since the complex obeys 18e––rule

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QUANTA POINT Sol-(1) /18e- Rule Applications & 16e-Rule
 z + 3 + 5 + 2 × 5 = 18 ( CNR  2e–)
z + 18 = 18
z=0
21. 1 and 5 are stable than 3 and be belongs to 2nd period and follows 8 e– rule.
Or we can say TVE in this complex
[Be(1–C5H5)(5–C5H5)] = 2 + 1 + 5
= 8e– (stable)
22. [(6 – C6H6)nCr(CO)m]
=1×6+6+2×3
=6+6+6
= 18 e
Correct option is (b)

5

23. A

3

TEC of complex
5 + 3 + A = 18
A = 18 – 8
A = 10 e–
 Ni is the right answer.
24. The complex having 17e– count or we can say less than 18e– do reduction and act as oxidising agent.
In option ‘b’ we have V(CO)6 = 5 + 6 × 2
= 17e–
 V(CO)6 + Na  Na+[V(CO)6]– 18e–
25. TEC in option b is–
8+6+6
 20e–
26. TEC = 3 × 2 + 9 + 3 × 2 + 9 + 3 × 2
=6+9+6+9+6
= 36e–.
Or we can say 18e– count on each Rh metal.
27. TEC = 5 + 4 + x + 2 × 2 + 1 = 18
9 + x + 4 + 1 = 18
x = 18 – 14
x=4
 Metals are Ti/Zr/Hf having e––count 4.

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QUANTA POINT Sol-(1) /18e- Rule Applications & 16e-Rule
But ans is ‘Zr’ as asked for second transitor series metal.

28. NO contains one more electron than CO in N – O * orbital and thus act as a three electron donor, i.e. linear
NO.
However, NO can also act as one electron donar when the lone pair resides on the nitrogen and the geometry is
in the bent form.

NO+ isoelectronic CO
29. 5 + 6 – 1 = 10 4 + 6 = 10
Linear molecular geometry Linear molecular geometry
N O C O
30. Since the complex obeys 18 e– – rule
 [Ni(CO)3(NO)]x has total electron count as –
10 + 3 × 2 + 3 + x = 18
10 + 6 + 3 + x = 18
19 + x = 18
x = –1
So, the correct answer will be +1 as we know the charge will be of opposite sign to that of calculated by the
formula.
31. Linear is sp hybridised and bent is sp2 hybridised
32. Linear molecule having sp hybridization
2–
M N O M N O
become almost
double bond.
Bent having sp2 hybridization
M N
O
double bond
 option ‘c’ is the right ans.
33. Linear mode
2-
M N O M N O
 bond (M – N bond)
Bent mode
M N  – bond
O
isoelectronic
Fe(CO)2(NO)2 Fe(CO)5
34.
8 + 4 + 6 = 18 e – 8 + 10 = 18 e–
35. N2 is the colourless gas that is liberated.
 The product must be a dimer as it has CN = 5 and it can dimerise to form CN – 6. Since, the new complex
obeys the 18 e– – rule therefore Cl atom must be at bridge

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QUANTA POINT Sol-(1) /18e- Rule Applications & 16e-Rule
Structural
L Cl L
L L
Re Re
L L
L Cl L
TEC = 7 × 2 + 3 × 2 + 2 × 8
= 14 + 6 + 16
= 36
 Each Re has 18 e– and there is no M – M bond present.
36. Dinitrogen can bind with metal in a number of different ways. The majority of complexes have terminal monohapto
link, 1 – N2 in which the bonding can be considered to be like that of isoelectronic CO ligand.
37. TEC of [CoCl(en)2(NO)]+
 9 + 1 + 2 × 4 + x – 1 = 18
 x + 17 = 18
x = 18 – 17
x=1
 Bent form
TEC of [Co(diars)2NO]+2 is
 9 + 8 + x – 2 = 18
 15 + x = 18
 x = 18 – 15
x=3
 Linear form

38. TEC = 9 × 9 + 5 + 21 × 2 + 2
= 81 + 5 + 42 + 2
= 130 e–
 It’s geometry is capped square anti-prismatic
39 TEC = 6 × 8 + 17 × 2 + 2 × 3
= 48 + 34 + 6
= 88 e–
PEC = TEC – 12 × n
= 88 – 12 × 6
= 88 – 72
= 16 e–
PEC 16
  8 pairs
2 2
i.e. (n + 2) Nido
(6 + 2)

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QUANTA POINT Sol-(1) /18e- Rule Applications & 16e-Rule
40. (5  C5 H5 )Co  BH
Isolobal

5  9  14e  3  1  4e 
 complex become BHB4H10
 B5H11 = (BH)5H6
5 2  6

2
10  6

2
16
  8 pairs
2
Correct option is (d)
H H +
Ph
+ C Ph
41.
Mo Ph Mo Mo
Hydride
OC CO CO acceptor
OC CO CO OC CO CO
42. a, b, c all are used as anti-knocking agents.

43.
Cu
CO

TEC = 5 + 2 + 11
18e–

(b)
V
CO CO
CO CO

TEC = 5 + 5 + 2 × 4
= 10 + 8
= 18e–
44. Because vitamin B12 CO-enzyme and Ni(CO)4 is an organometallic compound.
45. Organometallic compounds can be used as all four of them.
46. In option ‘c’ NO behave as bent and in option ‘b’ NO behave as linear and hence obeys 18e ––rule and are
formed by the given combination.
TEC = 6 + 5 + 3 + 3 + 1

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QUANTA POINT Sol-(1) /18e- Rule Applications & 16e-Rule
= 18e–
47. (a) TEC = 9 + 2 + 1 + 2 × 2 = 16e– (b) TEC = 9 + 1 + 3 × 2 = 16e–
(c) TEC = 10 + 4 + 2 = 16e– (d) cis-PtCl2(NH3)2= 10 + 2 + 2 × 2 = 16e–
48. ‘c’ is incorrect the rule is not applicable for main group as well as lanthanide and actinides metal, organometallic
complex.
‘d’  Eg-Cp2TiCl2, WMe6, CpWOCl3, etc, A possible reason for the same is that some of the orbitals of these
complexes are too high in energy for effective utilization in bonding or the ligands are mostly -donors.
49. Obeying 18e– rule,
the TEC of [Mo(C7H8)(CO)3] is
 6 + x + 3 × 2 = 18
6 + x + 6 = 18
x + 12 = 18
x = 18 – 12
x=6
 hapticity will be 6
50. [Fe(NO)(CN)5]2–
TVE = 8 + 3 + 5 + 2
= 18 e
Here NO is in linear form charge of NO is + 1
O.S. = Fe + 1 – 5 = – 2
= Fe – 4 = – 2
= Fe = – 2 + 4 = +2
Correct answer is 2
51. TEC = 5 + 2 × 2 + 8 + 2 – 1
=5+4+8+2–1
= 18e–
52. TEC = 2 + 2 + 5 × 2 + 9 × 2
= 4 + 10 + 18
= 32e–
53. TEC = 10 + 3 × 3 + 1 + z = 18
 10 + 9 + 1 + z = 18
 20 + z = 18
 z = 18 – 20
z=–2
As we know the charge taken is of opposite sign of observed one.
54. TEC = 5 + 6 + 2 × 2 + 2
= 17e–
55. TEC = 9 + 3 + 2 × 2 + 1 + 1 = 18e
56. TEC of [Fe(CO)n]2– = 8 + 2 × n + 2 = 18

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QUANTA POINT Sol-(1) /18e- Rule Applications & 16e-Rule
 10 + 2n = 18
2n = 8
8
n=
2
n=4
 The complex become [Fe(CO)4]2–
57. TEC = 8 + 3 × 2 + 4
=8+6+4
= 18 e–
58. TEC = 5 + 7 + 3 × 2
= 18 e–
Correct answer is (18)

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Sol- (2) Metal -Metal Bond
HINTS & SOLUTION
1. TEC = 3 × 5 + 3 × 10 + 2 × 2 + z = 18 × 3
 15 + 30 + 4 + z + 6 = 54
 3M  Mbonds 

6e

 6 + 49 + z = 54
z = 54 – 55
z = –1
As we known the sign of the charge taken is opposite to the observed one
 the ans will be + 1 i.e. option ‘c’
2. TEC = 4 × 2 + 5 + 2 × 3 + 5 + 4 × 2
=8+5+6+5+8
= 32 e–
TEC
per M – M bonds  18 
n
32
 18 
2
= 18 – 16
=2
3. TEC = (2 × 2 + 9 + 1) × 2
= 14 × 2
= 28 e–
16  n  TEC
M – M bond 
2
16  2  28

2
32  28

2
4
 2
2

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QUANTA POINT Sol-(2) /Metal-Metal Bond
H

Rh Rh
Structure
H
4. TEC of the complex obeying 18 e– – rule is
4 + (M + 6 + 2 × 2) × 2 = 36 (4 due to M = M)
2M + 24 = 36
2M = 36 – 24
2 M = 12
12
M 6
2
 we have Cr | Mo | w metal taking palce:

CO
OC Cr Cr CO
structure
OC

5. TEC = 7 × 3 + 3 × 3 + 2 × 12
= 21 + 9 + 24
= 54 e–
18  3  54
M – M bond 
2
54  54
 0
2
There is no. M – M bond in this complex.
(CO) 4
Mn
H2P PH 2

(OC)4Mn Mn(CO)4
P
H2

obeys 18 e–
6. Ir H 9 + 5 + 1 + 1 + 2 = 18 e–
H
PMe3
7. TEC = 2 + (5 + 7 + 2 × 2) 2
= 2 + 16 × 2
= 34e–
TEC
per M – M bond  18 
n

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QUANTA POINT Sol-(2) /Metal-Metal Bond
34
 18 
2
= 18 – 17
=1
8. TEC = 2 + 4 × 8 + 12 × 2 + 2
= 2 + 32 + 24 + 2
= 60 e–
60
per M – M bond  18 
4
= 18 – 15
=3
9. TEC = 5 × 2 + 7 × 2 + 2 × 2 × x + 4 = 18 × 2
 10 + 14 + 4 + 4x = 36
 
28 + 4x = 36  Mn  Mn 
 
4x = 36 – 28  e count
 
  4 
4x = 8
x=2
 The complex will become

CO
CO Mn Mn CO
CO

10. To find M – M bond we have,

18  n  TEC
M – M bond =
2
 TEC = 8 × 2 + 6 × 2 + 2 × 2 = 16 + 12 + 4 = 32e–
18  2  32 36  32 4
Now, M – M bond =   = 2.
2 2 2
11. Oxidation state of [Ni2(CO)6]2– is
2x + 0 = –2
x = –1
18  n  TEC
Now, M—M bond =
2
TEC = 10 × 2 + 6 × 2 + 2
= 20 + 12 + 2
= 34e–
18  2  34
 M—M bond =
2

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QUANTA POINT Sol-(2) /Metal-Metal Bond


= 36  34  2  1
1

2 2
 The structure will be—
2–
CO CO

CO Ni Ni CO

CO CO
12. TEC = 5 × 2 + 9 × 2 + 1 × 2 + 2 × 2
= 10 + 18 + 2 + 4
= 34e–
18  n  TEC
 M—M bond =
2
18  2  34
=
2
36  34 2
=   1
2 2
 The structure will become
H 3C Cp*
Rh Rh
Cp* CH3
13. TEC = 7 × 2 + 4 × 2 × 2 + 3 × 2 (2-Br = 3)
= 14 + 16 + 6
36e–
18  2  36
 M—M bond =
2
36  36
=  0
2
There is no M—M bond b/w Mn which means the structure will be
Br
(OC)4Mn Mn(CO)4
Br
14. TEC = 2 + 2 + 5 × 2 + 9 × 2
= 4 + 10 + 18
= 32e–
18  n  TEC
M—M bonds =
2

18  2  32 6  32 4
=   = 2.
2 2 2

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QUANTA POINT Sol-(2) /Metal-Metal Bond
 Structure becomes,
H2
C
Cp Rh Rh Cp
C
O
15. TEC = 5 + 2 + 8 + 2 × 2 + 8 + 2 + 5
= 34e–
18  n  TEC
M—M bonds =
2

18  2  34 36  34 2
   =1
2 2 2
16. Example [Re2Cl8]2–
Cl Cl 2–
Cl
Cl
Re Re
Cl
Cl Cl Cl
The Quadruple Re – Re bond is made of one -bond two -bonds and one -bond.
17. [Cp* Ru (µ3 – Cl)]4
VE = 5 × 4 + 8 × 4 + 4 × 5 = 72
N  18  VE
K=
2
4  18  72 72  72
=  0
2 0
There is no metal-metal bond present.

Ru Cl
Cl Ru

Cl Ru
Ru Cl

Correct option is (a)

18. [Cp2Ni2 (µ – Br)2]
VE = 10 + 20 + 6 = 36

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QUANTA POINT Sol-(2) /Metal-Metal Bond

n  18  VE
K=
2
2  18  36
=
2
36  36
=
2
=0
There is no M – M bond present.
Br
Ni Ni
Br
19. (µ – H2) [( – C5H5)(NO) W(OH)]2
2 5

VE = 2 + 10 + 6 + 12 + 2 = 32
n  18  32 2 18  32 36  32
K=  
2 2 2
4
= 2
2

H
W W
N N
O H
O
Correct option is (b)
20. [CO)3Ni – Co(CO)4]z
Z + 3 × 2 + 10 + 9 + 3 × 2 + 2 = 36
Z + 6 + 10 + 9 + 6 + 2 = 36
Z + 33 = 36
Here A (TVE = 33) which is 3e lesser than 36 hence to make equal, complex should be reduced by 3e i.e. Z
= – 3.
So, correct option is (a)
OCH3
21. (CO)5M C
Ph
10 + M + 2 = 18
12 + M = 18
M = 18 – 12
=6
M = 16 Cr, Re+
Correct option is (a)
22. Metal–Metal bond is not possible or only weak interactions in d8 – d8 configuration.
Eg. Ni(CO)4 (LNCC)

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QUANTA POINT Sol-(2) /Metal-Metal Bond
Correct option is (d).
23. As the size of the metal increases, the tendency of bridge forming decreases. So, in Ir4(CO)12 there is no bridging
ligand.
Correct option is (a).

O
CO C
OC CO OC CO
24. OC Co Co CO Co Co CO
OC
OC CO CO
CO OC C
O
Solution Solid

Correct option is (b).

OC OC COCO
Fe
OC O CO
25. C
OC Fe Fe CO
OC C CO
O
Correct option is (b)
26. O.S. = – 1 + x + 0 = 0
x  1
 d – electron count will be (7 – 1) = 6
TVE = 5 + 7 + 3 × 2
= 18 e–
18  1  18
M – M bonds  0
2
27. TEC = (5 + 3 + 6 + 1) × 2 + 2
= 15 × 2 + 2
= 30 + 2
= 32 e–
18  2  32
M – M bonds =
2
36  32
 2
2
32
Per M-M bonds  18 
2
= 18 – 16 = 2
Structure

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QUANTA POINT Sol-(2) /Metal-Metal Bond
H H H
Cp W W Cp
ON H NO
28. TEC = 4 × 9 + 12 × 2
= 36 + 24
= 60
60
per M – M bonds  18 
4
= 18 – 15
=3
29. TEC = 2 × 8 + 9 × 2
= 16 + 18
= 34 e–
Electrons towards cluster bonding
= 34 – 12 × 2
= 34 – 24
= 10 e–
30. TEC = 5 × 2 + 1 + 4 + 8 + 2 × 2 + 5
= 10 + 5 + 8 + 4 + 5
= 32 e–
18  2  32
 M—M bond =
2
36  32
=
2
4
= =2
2
2 Zr-Ru bonds are calculated but actually only 1 bond is observed.

CO
CO
Zr Ru

Ot-Bu
31. TEC = 3 × 2 + 10 × 2 + 1 × 2 + 2 × 2
= 6 + 20 + 2 + 4
= 32e–
Since, this is a square planar structure so the formula of M—M bond will be
16  n  TEC
M—M bond =
2

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QUANTA POINT Sol-(2) /Metal-Metal Bond
16  2  32
=
2
32  32
=  0
2
structure will be.
Cl RC
Cl
CR
Pd Pd
RC
Cl Cl
CR
32. Let the O.S. of the two W atoms are x and y.
x+y–6=0
x+y=6
x=3 y=3



W3+ = d3 W3+ = d3 




The configuration will be 24

Bonding  Anti bonding
B.O. 
2
60

2
=3
33. TEC = (5 + 6 + 3 × 2) × 2 = (5 + 6 + 6) × 2
= 17 × 2 = 34 e–
18  n  TEC 18  2 – 34
M — M bonds = 
2 2
36  34 2
=   1
2 2

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Sol- (3) Clusters
HINTS & SOLUTION
1. (a) C2B3H5  (BH)2B3H5
= (B5H5)H2
=5×2+2
= 12 e–
(b) C2B4H6  (BH)2B4H6
= (B6H6)H2
=6 ×2+2
= 14 e–
(c) B5H9  (BH)5H4
=5×2+4
= 14 e–

 PCB9 H11   P  BH 2 unit 


  BH 2  BH  B9 H11 

2.

  BH 11 H 3  or [B11H11]4– uinit (Nido)
11 2  3  1

2
22  4

2
26
  13 i.e.  n  2   Nido 
2 
11 2 

3. Fe4C(CO)13 electron count is

TEC = 4 × 8 + 4 + 13 × 2
= 32 + 4 + 26
= 62 e–
PEC = 62 – 12 × 4
= 62 – 48
= 14
PEC 14
 7
2 2
i.e.  n  3 Arachano

 4  3
4. Os6(CO)18 electron count will be

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= 6 × 8 + 18 × 2
= 48 + 36
= 84 e–
PEC = 84 – 12 × 6
= 84 – 72
= 12
PEC 12
  6 i.e. (n) (hyper closo)
2 2
and when we add 2e– complex become
[Os6(CO)18]2– and TEC = 86
 PEC = 86 – 72 = 14
PEC 14
   7 i.e. (n + 1) closo (6 + 1)
2 2

5. SiC2B4H10  (BH)(BH)2B4H10  Si  BH unit 

= (BH)7H6
72  6

3
14  6

2
20
  10 i.e. (n + 3)
2
Arachno (7 + 3)
6. TEC = 8 × 3 + 12 × 2
= 24 + 24
48e– (14n + 6)
PEC = TEC – 12 × n
= 48 – 12 × 3
= 48 – 36
= 12
PEC 12
 = 6 (n + 3) i.e. (3 + 3)
2 2
 Os3(CO)12 is Arachno metal cluster.
7. TEC = 7 × 7 + 4 + 21 × 2 + 3
= 49 + 4 + 42 + 3
= 98e–
PEC = TEC – 12 × n
= 98 – 12 × 7
= 98 – 84
= 14
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QUANTA POINT Sol-(3) /Clusters

PEC 14
 = 7 (n)
2 2
A 98e–, seven metal cluster is two electrons short of a closo configuration. The structure would be expected to be
capped closo or hyper closo.
8. We can write C2 as (BH)2 unit
 C2B4H8 becomes (B2H2B4H8)
No. of skeletal electron pairs = B6H10
= (BH)6H4 or [B6H6]4– (Nido)
6 2  4
=
2
12  4
=
2
16
=
2
= 8 i.e. (6 + 2)  (n + 2) Nido
9. C2B3H7  (BH)2B3H7 ( C = BH unit)
= (B5H5)H4 or (B5H5)4– (Nido)
5 2  4
=
2
10  4
=
2
14
= = 7 pairs
2
i.e., (n + 2) (5 + 2) Nido
10. [SB10H10]2–  [BH3B10H10]2– ( S = BH3)
= [(BH)11H2] 2–
or (B11H11) (Nido)
4–

11  2  2  2
=
2
26
=
2
= 13 pairs i.e. (n + 2) (11 + 2) Nido
11. As2C2B7H9  (BH2)2(BH)2B7H9
= (BH)11H4 or (B11H11)4– (Nido)
11  2  4
=
2
22  4 26
=  = 13 pairs
2 2
i.e. (n + 2) (11 + 2) Nido
12. Ge94  9  4  4

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QUANTA POINT Sol-(3) /Clusters
= 36 + 4
= 40 i.e. (4 × 9 + 4)  (4n + 4) Nido
Correct option is (b)
13. Let the O.S. of the two Os atoms are x and y.
x+y–8=–2
x+y=–2+8
x+y=+6
x=+3 y=+3
i.e. Os = 5d Os3+ = 5d5
3+ 5

Therefore, total number of d-electrons on Os3+ are

5 + 5 = 10
Electronic configuration in this cluster ion is 242*2
82 6
Bond order   3
2 2
and have staggered geometry.
*

*



*









Correct option is (c)
14. 74 e– count have square pyramid geometry.
Correct option is (b)
15. Os3(CO)12 Br2 have TEC
= 3 × 8 + 2 × 12 + 2
= 24 + 24 + 2
= 50 e–
 it does not follows correct total electron count having geometry trimer.
The geometry for 50 e– count is acyclic trimer.
Correct option is (a)
16. Octahedral fragments 
Isolobal
Square planer fragments
ML n ML n  2

Fe(CO)4 
Isolobal
Pt (PR 3 ) 2

d8 d10
L L L
Isolobal
M M
L L L
Pt(PR3)2 Fe(CO)4
Correct option is (b)
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QUANTA POINT Sol-(3) /Clusters

17. [Fe(CO)2 (PPh 3 )] 

Isolobal
CH
8  2  2  2 1 4  1  5e 
 15e 

Correct option is (a)

18. Ni (PPh 3 )2 

Isolobal
BH [ C  BH ]
10  4  14 e  3  1  4e
C2B4H6 Ni (PPh3)2 becomes (BH)2B4H6BH
 [B7H9] = (BH)7 H2 or [B7H7]2– unit (Closo)
72  2

2
14  2 16
   8 pairs
2 2
i.e. (n + 1) closo  (7 + 1)
Correct option is (a)
19. Rh Cp CO = 9 + 5 + 2
= 16 e–
Which is isolobal with 6 e– species
 CH2 have 6 e–
Can also be represented as
H2
C

CH2 CH2
Correct option is (b)
CO CO
20. Fe
CO
=8+3×2+3
= 17 e–
which is isolobal with 7 e– species.
CH3 = 3 + 4
= 7 e–
CO CO CO
Isolobal
Fe Fe CH3 CH3
CO OC CO
Correct option is (a)
21. In Bi 32 = 3 + 3 × 5 + 2
= 3 + 15 + 2
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QUANTA POINT Sol-(3) /Clusters
= 20 e– i.e. (4n + 4) Nido
Correct option is (b)
22. Ru(CO)3 
 BH unit

8  3  2  14e 3  1  4 e
 The complex become.
C2B9H11Ru(CO)3 = (BH)2 B9H11BH
= B12H14 or [B12H12]2– unit (Closo)
= (BH)12H2
12  2  2

2
26
 = 13 i.e. (n + 1) closo (12 + 1)
2
Correct option is (b)
23. Mn(CO)3 
 B unit

7  3  2  13 e 3 e
 The complex become
B3H8Mn(CO)3 = B3H8B
= B4H8 or [B4H4]4– unit (Nido)
= (BH)4H4

4 2  4

2
8  4 12
   6 pairs
2 2
i.e., (n + 2) Nido  (4 + 2)
Correct option is (b)
24. (A) TEC of [V(CO)6] = 5 + 6 × 2
= 5 + 12
= 17 e–
(B) [Cu(5– C5H5) (CO)] = 11 + 5 + 2
= 18 e–
(C) [Co(CO)4]– = 9 + 4 × 2 + 1
=9+8+1
= 18 e–
(D) [IrCl(CO) (PPh3)2] = 9 + 1 + 2 × 2 + 2 = 16 e–
 B and C are isoelectronic having 18 e–.
Correct option is (b)
25. Os3(CO)12  48e–  Triangular
Os3(CO)12  50e–  Linear
26. Os4(CO)16  8 × 4 + 16 × 2

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 32 + 32 64 Sq. planar
Os4(CO)14  8 × 4 + 14 × 2
 60 + Tetrahedron
27. (1) [Os6(CO)18]2– × 6 × 8 + 18 + 2 + 2 = 48 + 36 + 2 = 86  Octahedral
(2) Os6(CO)18  6 × 8 + 18 × 2  84  Capped TBP or bicapped tetrahedron
28. TEC = 5 × 8 + 4 + 15 × 2 = 40 + 4 + 30 = 74e–
Hence, have square pyramid geometry.
Correct option is (b).
29. (a) B10H14 = (BH)10H4
10  2  4

2
24
= 12 i.e. (10 + 2) (n + 2) Nido
2
(c) C2B9H12– = (BH)2B9H12–
= B11H14–
= [(BH)11H3]–
11  2  3  1
=
2
22  4
=
2
26
= = 13 i.e. (11 + 2)  (n + 2) Nido
2
(d) C4B2H6 = (BH)4B2H6
= B6H10
= (BH)6H4
6 2  4
=
2
12  4
=
2
16
= = 8 i.e. (6 + 2)  (n + 2) Nido
2
30. ‘b’ option is wrong as the no. of electrons available in Rh4(CO)12 are—
TEC = 4 × 9 + 12 × 2
= 36 + 24
= 60
PEC = 60 – 12 × 4
= 60 – 48
= 12 (Cluster bonding e–)
PEC 12
 = 6 pairs
2 2
31. ‘b’ option is wrong because
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QUANTA POINT Sol-(3) /Clusters
TEC = 6 × 8 + 18 × 2
= 48 + 36
= 84e–
PEC = 84 – 12 × 6
= 84 – 72
= 12 (cluster-bonding electrons)
PEC 12
 = 6 pairs
2 2
i.e. equal to ‘n’.
 its structure is hyper closo or capped closo.
32. [B11H11]4– unit (nido)
33. TEC = 6 × 8 + 4 + 17 × 2
= 48 + 4 + 34
= 86 e–
PEC = 86 – 12 × 6
= 86 – 72
= 14
PEC 14
  7 i.e. (n + 1) closo
2 2
(6 + 1)
It’s shape is octahedral
Isolobal
34. Au–PPh3 CH3

H Mn(CO)5
Since Au is stable in its +2 oxidation state, and have only 1 e– to interact and hence CH3, H and Mn(CO)5 also
have only 1 e– to interact.
Correct options are (a, b and d)

35. (a) Me–Mn(CO)5 Me–Me

Me 
Isolobal
Me Mn(CO)5 
Isolobal
Me
7 e 7 e 7  10  17 e  7 e

(b) OC=CH2 OC=Mo(CO)5

OC 
Isolobal
CO CH 2 
Isolobal
Mo(CO)5
4  2  6 e 6  10  16 e 

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QUANTA POINT Sol-(3) /Clusters

(c) C2H4 Fe(CO)3

(d) (CO)12Ir4 C4H8

Correct options are (a, b)

H
C 4 + 1 = 5e–
36. HC CH which is isolobal to 15 e–
C
H
(i) P4
–
P 5e

P P Isolobal to C4H4
P
(ii) Ir4(CO)12 (CO)3  9 + 6 = 15e–
Ir
(OC)3Ir Ir(CO)3
Ir
(CO)3
Correct answer is (2)
37. TEC = 2 + 3 × 8 + 10 × 2 = 2 + 24 + 20 = 46e–

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Sol- (4) Corbonyl
HINTS & SOLUTION
1. Free CO has the highest frequency and then when CO gets attached with metal or bridged with metals the
stretching frequency gets decrease as when CO bridges with metals, all metals can contribute electron density
into * orbital of CO to weaken the C – O bond and lower the energy of the stretch.
Correct option is (c)
2. Since PMe3 is electron donating group
PMe3
CO CO
Cr
OC (B.B.) CO
CO

Hence cis have greater CO frequency

Correct option is (a)
3. Generally Mn gives [Mn2(CO)10], Fe gives [Fe2(CO)9], & Co gives [Co2(CO)8], but Cr do not gives such type
of carbonyl complex. So its would not give homoleptic polynuclear complex but yes it will give heteroleptic
polynuclear complex.
Correct option is (c)
4. The back bonding is more in V(CO) 6 than V(CO)6 because of the additional negative charge on V, which
decrease the bond order of CO and increase the bond order of V–C, and decrease the bond length.
Correct option is (c)
5. Greater the negative charge on metal greater wil be the -back bonding.
Correct option is (c)
6. The formal oxidation state of Zr is +4 in (a) and +2 in (b). Lesser the +ve charge greater the  back bonding and
lesser the CO frequency.
7. The best donor will lead to the shortest M–C bond or we can say best -acceptor in the above three will lead to
have greatest bond length.
Correct answer is (d)
8. TEC = (5 + 8 + 2) × 4
= 15 × 4
= 60 e–
18  4  60
M  M bond 
2

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QUANTA POINT Sol-(4) / Carbonyl
12
 6
2
vCO = 1640 (given)
which means CO is bridged with three metals.
Correct option is (b)
9. Because negative charge on metal increase size of d-orbital. Therefore polarisation of d-orbital increases conse-
quently donar ability of metal increase. Therefore back bonding in CO increase. Consequently metal carbon
bond becomes strong and CO bond becomes weak.
Correct option is (b).
10. vCO of A at 1960 cm–1 means that all carbonyls are similar and terminal.
[-5CpMo(CO)3 ]2  (5  6  3  2)  2
= 17 × 2
= 34 e–
18  2  34
M  M bond 
2
=1 M – M bond
 vCO of B at 1850 cm–1 means all the CO are bridged.
[-5CpMo(CO) 2 ]2  (5  6  2  2)  2
= 15 × 2
= 30 e–
18  2  30
M  M bond 
2
36  30
2
6
 3
2
Correct option is (b)
11. Cr(NO)4 = 6 + 4 × 3 = 6 + 12 = 18e
Co(NO)3 = 9 + 3 × 3 = 9 + 9 = 18e
Correct option is (a).
12. Since spectrum of compound B at 1798 cm–1 means CO is bridged with 2 metals
And to attain 18e– (stable) in B compound dimerization will take place with the formation of a Co – Co double
bond.
Correct option is (b)
13. When a Lewis acid co-ordinates to the oxygen of CO which is already bound to a metal, more electron density
is pulled out from the group. This will increase back-bonding and hence vCO will decrease.
Correct option is (a)
14. -acceptor order is
PF3 > P(OMe)3 > PPh3 > dien > Py
Correct option is (b)

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QUANTA POINT Sol-(4) / Carbonyl

Br

15. OC Fe 2CO + Fe
OC Fe
CO CO
(A) (B)

OH
(CO)4Fe C O OH (CO)4Fe C
16.
O
OH -hydride elimination
(CO) 4Fe C (OC)4 Fe C O [HFe(CO)4]
O H O
17. V(CO)6 is 17e -system and will prefer associative mechanism and [V(CO)6]– is 18e– electron system and will
–

prefer dissociative mechanism. Since CO is more tightly bound in [V(CO)6]– which have high back donation due
to large electron density and hence [V(CO)6]– will be less reactive than V(CO)6.

Cl OC Mn h
18. (CO)5Mn Na + CO –CO Mn CO
OC OC
CO CO CO CO

Br (OC) Co
19. (CO)4Co – Co(CO)4 + 2Na  [Co(CO)4]– 4 h
Co(CO)3

CO –
2– OC
OC CO
20. +R—X Fe R
Fe
OC
OC CO CO
(P)

CO –
OC
L (CO)3Fe L
1, 1-Migration Fe
OC O R
O R

CO P CO
OC CO Ph2P Ph2 CO
21. Mo CH2 Mo
Ph2P P
OC
CO
CO
Ph2 CO CO

22. The overall effect is synergistic. CO can donate electron density via a -orbital to a metal atom, the greater the
electron density on the metal, the more effectively it can return electron density to the * orbitals of CO.

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QUANTA POINT Sol-(4) / Carbonyl
M(d) CO( *)

C O C O

C(lone pair) M(d)

CO to M–donation M to CO –donation
Correct option is (c).
23. In free CO, the electrons are polarized towards the more electronegative oxygen. For example, the electrons in
the -orbitals are concentrated nearer to the oxygen atom than to the carbon.
The presence of a transition metal cation tends to reduce the polarization in the C – O bond by attracting the
bonding electrons.
   
C O Mn+ C O
The consequence is that the electrons in the positively charged complex are more equally shared by the carbon
and the oxygen, giving rise to a stronger bond and a higher energy C – O stretch.
Correct option is (a).
24. In cases in which CO bridges with metal, all metals can contribute electron density in * orbitals of CO to
weaken the C – O bond and lower the energy of the stretch.
Correct option is (a).
25.  Na  [Mn(CO)5 ]–
Mn 2 (CO)10  Na 
OS  –1
Mn 2 (CO)10  Br2 
 (CO)5 Mn — Br
OS = +1
 Product A will have more -back bonding due to which C — O stretching frequency decreases.
Correct option is (b).
26. Tendency of CO to bridge metals decreases in going down the periodic table, as the orbitals of bridging CO are
less able to interact effectively with transition metals as the size of the metals increases.
27. Sulfur is less electronegative than oxygen. Therefore, the tungsten in W(S) Cl2 (PMePh2)2 has greater electron
density and a greater tendency to participate in -backbonding with CO, therefore the CO of [W(S) Cl2 (CO)
(PMePh2)2] is lower than [W(O) Cl2(CO) (PMePh2)2].
Correct option is (b).
28. Order of -acceptor ligands.
(C6F5) > (p – C6H4F) > (p – C6H4Me) > (t – C4H9)
29. Greater the negative charge on metal greater will be -back bonding and hence lesser will be the C – O stretch-
ing frequency,
Or, more the positive charge more will be the stretching frequency of CO.
Correct option is (a).
30. C – O order  PF3 > PCl3 > PClPh2 > PMe3 -accepting ligand increases stretching frequency of CO.
So, correct option is (b).
31. M(CO)4L
in this L are present on axial
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QUANTA POINT Sol-(4) / Carbonyl
L
CO
OC M
= C3v = 3
CO
CO
In this L are present on equatorial
CO
L
OC M
= C2v = 4
CO
CO
Correct option is (c).
32. Isocarbonyl bonding generally found in Al |Ti| lanthanoids –
AlCl3
M C O M C O Al
4
The electron count will be  , two from carbon and 2 from oxygen.
33. Among the following only Fe can form metal carbonyl complex in normal condition
34. Metal in low oxidation state bind more strongly and in high oxidation state binds least strongly, in (b) option Mo
is zero oxidation state and in (c) option Ti is in +4 oxidation state.
Correct option are (b) and (c).
35. Correct options are (a, b, d)
36. Ni(CO)4 = 10 + 8 = 18e = tetrahedral
[Cr(CO)4]4– = 6 + 8 + 4 = 18e = tetrahedral
[Mn(CO)4]3– = 7 + 8 + 3 = 18e = tetrahedral
[Co(CO)4]– = 9 + 8 + 1 = 18e = tetrahedral
37. ‘b’ option is wrong as the no. of electrons available in Rh4(CO)12 are—
TEC = 4 × 9 + 12 × 2
= 36 + 24
= 60
PEC = 60 – 12 × 4
= 60 – 48
= 12 (Cluster bonding e–)
PEC 12
 = 6 pairs
2 2
38. ‘b’ option is wrong because
TEC = 6 × 8 + 18 × 2
= 48 + 36
= 84e–
PEC = 84 – 12 × 6
= 84 – 72
= 12 (cluster-bonding electrons)

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QUANTA POINT Sol-(4) / Carbonyl
PEC 12
 = 6 pairs
2 2
i.e. equal to ‘n’.
 its structure is hyper closo or capped closo.
39. The general formula of C4V symmetry for finding IR bands is (n–2) (n = no. of CO present).
 (4 – 2) = 2
Correct answer is (2)

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Sol- (5) Carbene & Carbyne
HINTS & SOLUTION

X Hetero atom
1. LnM C* (OR, NR2)
Y
Singlet carbene

X X
M C M C
Y R
Due to the overlapping of hetero atom the bond order in Fischer carbene of metal and carbene carbon is between
one and two.
2. In Fischer carbene, metal is in low oxidation state.
 Carbene carbon is electrophilic in nature.
 The organic carbene used is singlet carbene.
3. Grubb’s catalyst is intermediate in between fischer & schrock carbene.
Pcy3
Cl
Ru
Cl H
Pcy3
Grubbs first generation catalyst.

OMe
(CO)5Cr C + NH2R
4.
E
Ph

OMe
NHR
H –MeOH
(CO)5Cr C (CO) 5Cr C
NHR Ph
Ph

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O O O
BuLi (CO) 5Cr C
(CO)5Cr C (CO)5Cr C
5.

O O
ClCH2OMe H+
(CO)5Cr C (CO)5Cr C + MeOH
–MeOH
H H 2C
H2C OMe
6. Bond order between double bonded carbon and its substituent depends upon electro-negativity of the substitu-
ent.
1
Extent of back donation  Bond order of C – M  Electronegativity 
B.O. of C – X
 Electronegativity order is
O > N > S.
Hence, option ‘a’ is the right answer.
7. Metal carbon IR stretching frequency depends upon the ligands present in the complex.
1
  acceptor ligands   C – X stretching frequency
M  C stretching frequency
Since in option (d) Py is good donor which means -back bonding between M and C will occur and due to
which M – C bond order will be strong and C – X bond order will be weak or lowest.
Me
OMe H N
8. OMe Me (OC)5Mo
(OC)5Mo NHMe (OC)5Mo N

RO
OMe
9. (OC)5Cr C
OR (CO)5Cr C
E Ph OMe
Ph
OR
OR Ph
(OC)5Cr (OC)5Cr C 
C H MeO
Ph OMe
10. Singlet carbene is treated as neutral and there is no change in O.S. of carbene metal.

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QUANTA POINT Sol-(5) / Carbene & Carbyne
X

LnM C
Y

M C


11. R

M C
R
dionionic

M C

12. For terminal  250 - 500 
For bridging groups  100 – 210 with M – M bond
For bridging groups  0 – 10 without M – M bond
13. The Cr – C bond length is longer is II as compared to I as the carbene carbon is electron deficient in both the
cases. However, in I there is only one hetero atom containing electron donating group while in II there are two
heteroatom based electron donating groups on the carbene carbon. The effect of the phenyl group seems to be
less when compared to the heteroatoms.
14. In fischer carbene metal atom is relatively electron rich & metal carbon bond has relatively low rotational barrier.
In schrocks carbene it behave like phosphorus ylide in some of its reaction, in this carbene carbon is nucleophilic
in nature and it does not obey 18e rule.

Et3OBF4– N
Cr(CO)6 + (OC)5Cr C O
15.
N

Li

O OEt
Et3OBF4
(OC)5Cr C (OC)5Cr C
N N

16. The fact that the carbonyl stretching frequency is lower in the carbyne complex indicates that the electron density
is more on the metal and the back donation to CO is higher. This means that the carbynes are better donor than
the carbenes.
17. Obeying 18e– -rule TEC = 1 + 2 × n + 7 + 2 = 18
 2n + 10 = 18
2n = 8
n=4

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QUANTA POINT Sol-(5) / Carbene & Carbyne

O
 The complex become (Br)(CO)4Re C
O

18. Option (a), (b), (c) and (d) all are correct most widely application of metal carbene is in olefin metathesis
reactions. So all type of reaction will take place.
19. Fischer carbene is stabilized by heteroatom or phenyl group whereas in schrock carben, the carbene carbon is
electron rich, attacked by electrophile & destabilized by hetero atoms.
In fischer carbenes the middle to late transition metals in low oxidation states are present where as in schrock
carbene the early transition metals in high oxidation states are present.
20. TEC = 2 + 2 + 5 × 2 + 9 × 2 = 4 + 10 + 18 = 32e–

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Sol- (6) Alkene +Alkyne
HINTS & SOLUTION
1. The C = C -bonding MO acts as an electron donor, while the  – MO is an electron acceptor.
2. Fullerene attached with metal through 2 mode.
Eg. Mo (2 – C60) (CO)5

Ha Ha
aH Rh
Ha
3.
Hb H b H b H
b
At low temperature i.e. 233K two signals of alkene proton are observed.
4Ha  1 signal
4Hb  1 signal
But at high temperature i.e. 373K, the proton environment become equivalent as each alkene ligand rotates
about the metal ligand co-ordinate bond. Therefore only 1 signal is observed.
8H 1 signal.

> > > > >

4.
most least
reactive reactive

MLn
MLn
5. O O

MLn
H H
H MLn R
O O MLn
O R

H H H
R
(R = nC6H`13)
6. Olefins such as a cyclohexenes have little or no ring strain and cannot be easily polymerised with the usual
catalysts. Strained cyclic olefins such as shown above, have sufficient ring strain to make this process possible.

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O
CF3
> > >
CF3

Nu Mo
Mo
7.

H2C Nu

Cp R2
P
R2 2+ Mo MeO
Cp P P
Mo MeO R2
8. P 2 eq
R2 OMe

OMe
R2
P
Mo
P
R2

MeO OMe
9. Tetraethyl lead i.e. Pb(C8H20) is not -bonded complex. It is -bonded organometallic compound.
H3 C
Pb
H3 C CH3
H3 C
10. In this series, (i) has the shortest C – C bond length, the back donation from Fe to ethylene is least because of
higher positive charge on the complex and the presence of two good -acceptor CO groups.
and (iv) has the longest C – C bond length indicating the highest back donation to ethylene due to the presence of
two good -donor Et3P groups.
11. The tungsten complex will bind most strongly since the third row transition metals binds the strongest and also due
to the presence of two highly donating biphosphines. Ti4+ has no electron density for back donation since it is a d°
system.
12. Trans cyclo-octene has more strain when compared to the cis-isomer and hence will bind strongly to metal to
release this strain.
13. As we know in the presence of EWG -back donation increases due to which M – C bond becomes strong and
C – C bond becomes weak.
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QUANTA POINT Sol-(6) /Alkene+Alkyne
Since in C2F4, F act as EWG hence have C – C bond weak and C – C bond length high.
14 [Ph3C]+ abstracts H–, then -hydrogen elimination takes place.

Fe Me [Ph3C] [BF4]
CO C Fe CH Me [BF4]– + Ph3CH
CO H C H CO
2 H
 CO H C
2

15. The extent of donation or back-donation depends on Metal, substituents present on alkene and ligands attached
with metal.
16. The presence of EWG’s on the alkene increases the strength of the metal-alkene bonding while EDG’s decreases
the stability.
17. Correct options are (a), (b) and (d).
Cl –
Cl
Pt
18.
Cl

TEC = 10 + 3 + 2 + 1 = 16e–
19. TEC = (7 + 3 + 4 × 2) × 3 = (7 + 3 + 8) × 3 = 18 × 3 = 54e–

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Sol- (7) Oxidative Add
HINTS & SOLUTION
1. Most commonly the metal in the complexes in their low oxidation states having d8 or d10 configuration are used for
oxidative addition reaction.
2. As we move down the group, the rate of oxidative addition reaction increases.
3. Increase in steric hinderance on carbon leads to decrease in the rate of oxidative addition reaction.
 MeI > EtI > i-PrI
4. The metal Ti is in the highest oxidation state (+4) and has no d-electrons present i.e. d°.

–CO CF3CF2I F3CF2C

Rh+1 Rh
5. Rh+3
OC CO OC
OC I
18e– 16e– trans
18e–
H
O CH2CH2R Ph3P H
PPh3 C Rh
Rh+1 + H2 OC PPh3
6.
OC C
PPh3 O CH2CH2R

16e– 18e–
7. Oxidative addition is the most important reaction pathway observed in square planar substitution.

8. Diborane reagents undergo oxidative addition to late transition metals such as Co, Rh, Ir, Pt, after dissociation of
phosphines or other labile ligands.
9. For given alkyl halide, rate of oxidative addition reaction increases with increasing basic character of metal.
10. The rate of oxidative addition increases with with decreasing steric crowding.

11. This is example of oxidative Coupling reaction. Because coupling take place in between metal and alkyne group.
Correct option is (b)
12. Ir(dmpe)(CO)Cl gives fast oxidative addition reaction because dmpe is better donar than dppe.
13. In (A) we have Co+ and Ir+
 [Ir(dppe)2]+ will be more reactive towards O.A. of dihydrogen, because as we move down the group rate

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increases.
In (B) we have PPh3 vs CO
As we know -acceptor ligand decrease the rate of O.A. reaction i.e. CO > PPh 3
 Rh(PPh3)2Cl will have greater reactivity.
14. Low oxidation state of metal complex can undergo oxidative addition reaction.
18 e– complex can also undergo oxidative addition reaction by removing or creating vacant site.
15. Steric hindrance and -acceptor ligands decreases the rate of oxidative addition reaction.

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Sol- (8) Reductive Elimination

HINTS & SOLUTION

1. Efficient for d8 metals Ni(II), Pd(II) and Au(III) and d6 metals Pt (IV), Pd(IV), Ir(III), Rh(III).
2. The formal oxidation state of the metal is reduced by two units in the reaction.
3. Generate a 5-coordinate intermediate, a much more reactive species than the starting 6-co-oridination complex.
H H
Cl L Cl L
Rh –L Rh
L R L R
L
4. After reductive elimination, a T-shaped 3-coordinate species is formed.
H H
Cl L –L Cl L –HR
Rh Rh L Rh L
L R L R
L Cl
T-shaped 14 e–
5. Reductive elimination is the reverse of oxidative elimination vice-versa.
If reductive elimination of 6-co-ord. d6 species goes then the reverse reaction, oxidative addition of 4 co-ord. d8
species is also expected to go.
6. The -acceptor ligands attached to metal will enhance the rate of reductive elimination reaction.
7. The presence of bulky groups or steric crowding facilitate the reductive elimination reaction.
8. Correct option is (b)
9. First row > Second row > Third row
This is due to the bond strength, the metal-ligand bonds in first row complexes being weaker than second and
third row metals.
10. The cis addition of PhSiH3 forms the intermediate which then undergoes reductive elimination of PhH2SiSiH2Ph.
H
SiH2Ph PhSiH3 SiH2Ph reductive elimination
Cp2Hf Cp2Hf
Cl Oxidative SiH2Ph
addition Cl
intermediate
H
Cp2Hf PhH2SiSiH2Ph
Cl

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O
I
OC C I CO
11. Rh CH 3 Rh + CH3C(O)I
OC I OC I
I

H Ph – H
Reductive Cp H Cp
oxidative addition – H2
12. Ta H Ta Ta H
Elimination Cp Reductive
Cp
H – H2 H elimination
Ta+5, 18 e– Ta+3, 16 e– 18 e–

Reductive Cp D
Cp D2 Cp elimination
Ta Ta Ta
Cp Oxidative Cp Cp
addition D
D Ta+3, 16e–
18 e–
13. (i) is an unstable complex having 15e–
(ii) the eliminating groups are trans to each other.
(iii) O.S is = x – 3 = 1
x=+1+3
x=4
O.S is Pt+4 and the metal is highly deficient, groups are cis to each other and also obey 18 e– rule.
14. Reductive eliminations from d0 early metal centers to form products containing metals possessing d2 electron
configuration are less common.
–CO
15. IrH2Cl(CO) (PPh3)2 h IrH2Cl(PPh3)2 –H2 [IrCl(PPh3)2] +CO [IrCl(CO)(PPh ) ]
3 2

OC CO OC CO Br
CO
+Br2
16. OC Mn Mn CO 2 OC Mn CO
OC CO OC CO OC
CO
it is an example of oxidative addition reaction.
Correct option is (d)
17. It is example of oxidative addition reaction. Because Au is oxidised when CH3I is added.
Correct option is (a)
18. All the above factors affect the rate of reductive elimination reaction.

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Sol- (9) Miqratary insention , Elimination
HINTS & SOLUTION
1. There is no change in oxidation state of metal in migratory insertion reaction.
Correct option is (c)
2. The given reaction is 1, 1 insertion indicating that both bonds to the inserted molecule are made to the same atom
in that molecule. In this reaction both Mn and CH3 are bonded to the sulfur of the inserted SO2.
3. Abstraction reactions are elimination reactions in which the Co-ordination number of the metal does not change.
In general, they involve removal of a substituent from a ligand, often by the action of an external reagent, such a
lewis acid.
4. SO2 is the only common ligand that can give both types of insertion, as a ligand, SO2 can be 1(S) or 2(S, O).
Correct option is (c)

R2 R2
P P CH3
5. Pt +CH4 Pt
P P H
R2 R2

The very electron rich, two co-ordinate, 14 e–platinum reactant was not spectroscopically observed but its
existence was inferred from the reaction products.

h +PPh3

6. Rh Rh
Rh
OC CO OC CO Ph3P CO CO
16 e
–CO

Ph
OC PPh3
Correct option is (d)
7. Option (d) is correct because Ti is present in highest oxidation state (+4). and in higher oxidation state system
oxidative addition is not possible.
Correct option is (d)
Cl
8. Ni Ni
Cl

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QUANTA POINT Sol-(9) /Miqratary insertion ,Elimination
Electron count per metal = 10 + 3 + 3 = 16 e
Correct option is (a)
9. Migratory insertions are usually favoured on more electron deficient metals.
Lewis acid such as AlCl3, BF3 or H+ can increase the rate of migratory insertion reaction.
F
R R F B R F
F
M C M C M C
B
OH O F
O
F
By binding to the oxygen, the lewis acid would be expected to stabilize the transition state and speed up the
reaction.
Correct option are (a, c)
10. 1,1-insertion occurs with –bound ligands such as CO.
Correct answer is (1)
11. 1,2-insertion occurs with 2–bound ligands such as H2C = CH2
Correct answer is (2)

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Sol- (10) Catalysis
HINTS & SOLUTION
1. Catalyst used for asymmetric hydrogenation will be [BINAP)3 [DIPAMP] etc.
Ox
id a
tiv
of e ad
C(O of

M dit
He ation

eI ion
)I
min
Eli

Tennessee Eastman
2. process Migratory
insertion

Co-addition
Correct option is (b)
3. Oxidative addition of MeI to [Rh (CO)2 I2]– having 16 e– count is the slower and rate determining step in the
reaction.
4. The CO migratory insertion step is faster than the oxidative addition.
5. For the rhodium catalyst oxidative addition of MeI is the rate determining step. And this is more facile in electron
rich anionic complex.
Hence, [Rh(CO)2I2]– > [Rh(CO)3L]
6. In synthetic gasoline zeolite acting as an acid catalyst is to eliminate water molecules from methanol.
ZSM 5
CH 3OH     CH 2  n  H 2O
The zeolite acts as an acid catalyst and eliminates water molecules from methanol.
7. Wilkinson’s catalyst — RhCl(PPh3)3
Speier’s catalyst — Hydrosilylation
Water gas shift catalyst — Zinc-copper oxide
Zeolite ZSM-5 catalyst — synthetic gasoline
8. The increased strength of the metal-ligand bonds on going from Rh to Ir results in the rate determining step being
methyl migration.
9. Oxidative addition of MeI is faster in cis– [Ir(CO)2I2]– than cis – [Rh(CO)2I2]–
10. Precipitation of IrCl3 does not occur as readily as precipitation of RhCl3.
11. Scheme summarizes the Fischer-Tropsch (FT) reaction, i.e., the conversion of synthesis gas into hydrocarbons.
A range of catalyst can be used (e.g. Ru, Ni, Fe, Co) but Fe and Co are currently favoured.

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Hydrocarbons (linear + branched alkanes and alkanes)
Fe Oxygenates (linear alcohols, aldehydes, esters and ketones)
CO2
CO + H2

Co
Hydrocarbon (linear + alkanes and alkenes) H 2O
12. In methanol carbonylation process 90% of the methanol was getting converted into acetic acid by this process
along with the formation of side products such as acetaldehyde and ethanol.
Correct option is (c)
13. The Co-catalyst is used in monsanto acetic acid process is iodide.
Correct option is (a)
CH3
C O
O
14. OC I Reductive
Rh H 3C C I
elimination
OC I
Correct option is (d)
15. Promoters used in cativa process are GaI3, [Ru(CO)3I3]–, [Ru(CO)2I4]2–, ZnI2, SiI4.
Therefore CH3I does not act as promoters in the cativa process.
Correct option is (d)
16. The precursors used in cativa process is IrCl3 and H2IrCl6.
Correct option is (c)

17. Hydroformylation (Oxo process) is the conversion of alkenes to aldehyde.

CH3CH = CH2 + CO + H2  CH3CH2CH2CHO
18. It is catalysed by cobalt and rhodium carbonyl complexes and has been exploited as a manufacturing process
since World War-II.
19. The active catalyst in the catalytic cycle of oxo process is HCo(CO)3.
20. The catalytic cycle of hydroformylation follows the order–1, 2-Migratory insertion, Oxidative addition, Reductive
elimination.
21. The oxidative addition of H2 to Rh(CO)(COCH2R) (PPh3)2 is the rate determing step. This is the only step in the
catalytic cycle where the formal oxidation state of Rh changes from +1 to +3.
22. The rate of the oxidation of ethylene is unaffected by the presence of copper.
23. HCo(CO)4  18e–
After dissociation of CO we get HCo(CO)3  16e–.
24. The electron-donating property of the phosphine also increases the rate of hydroformylation of the initially produced
aldehydes to form alcohols.
25. The second generation of hydroformylation catalysts consists of rhodium complexes containing phosphorus ligands.
26. The regioselectivities and rates of hydroformylation with cobalt catalysts were improved significantly by the
addition of phosphines to HCo(CO)4.
27. Rhodium is about 1000 times more active than cobalt, processes based on Rh catalysts operate at significantly
lower temperature and pressure than processes based on Co catalysts.

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28. The role of copper salt as co-catalyst in Wacker’s process is to reoxidise Pd(0) by Cu(II).
2–
Cl Cl H2C CH2 Cl Cl
Pd Pd CH2 + Cl
29. Cl Cl Cl
H 2C
it is similar to Zeise's complex
Correct option is (c)

30. Wilkinson’s catalyst is a compound with the formula RhCl(PPh3)3. The rhodium is able to form a 6-coordinate
complex, allowing it to selectively alkenes, which are double bonds. This allows molecules with several double
bonds to selectively reduce one of the double bonds.
RhCl (PPh3) 3
31. H2, benzene
TFE
32. Wilkinson’s catalyst will never be able to reduce benzene double bonds because Wilkinson’s catalyst will only
reduce the least hindered double bond and that is where the catalyst is able to fit.
33. Wilkinson’s catalyst only reduces double bond. It does not reduces other functional group and does not reduces
carbon-oxygen double bonds.

H2
+
34.

Major Minor
35. Here alkene can act as inhibitor as it may occupy the vacant co-ordination site reacted when triphenylphosphine
dissociates.
Yield is very high for Wilkinson catalyst with high selectivity under mild reaction conditions.
36. The rate limiting step in the mechanism is the insertion into the alkene which is limited by the severe steric
hindrance around the metal center.
Ph3P
Ph3P Cl –PPh3
Rh Cl
Rh
38. PPh3 Ph3P
Ph3P
14e–
16e– trigonal planar
Square planar

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QUANTA POINT Sol-(10) /Catalysis

38. Crabtree catalyst i.e. [Ir(COD)(Cy3P)Py]PF6 is also a homogenous catalyst used for the hydrogenation of alk-
ene.
R OH R OH
H2
crabtree catalyst

Me Me H
Due to chelation, hydrogen comes with same stereo as ‘OH’.
O O

crabtree catalyst
39.
H2/CH2Cl2

Br Br Br Br
As crabtree catalyst reduces olefins in the presence of other functional groups.
40. Co2(CO)8 does not used for the hydrogenation of alkenes, it is used in hydroformylation process.
R R R
41. > > >
R R
Wilkinson catalyst is good for cis-alkene in comparison of trans alkene and as the size and number of substituents
increases the rate of hydrogenation decreases.
Ph3P PPh3
42. Rh+1
Wilkinson’s catalyst
Ph3P Cl
Ox
ad idati
dit ve
ion
nation
Elimi tion
Reduc

43.
y
a tor
r
ig ion
M t
, 2- ser
1 in
Correct optio is (a)
44. Wilkinson catalyst can also lose PPh3 to give RhCl(PPh3)2, and dimerize via holide bridges and each of these
species have their own catalytic cycle.
Ph3P Cl PPh3
Rh Rh
Ph3P Cl PPh3

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Correct option is (a)
L
Ph3P Cl Ph3P L
+1 2L
Rh Rh
45. Cl
Ph3P PPh3 Ph3P
PPh3
Correct option is (b)
46. Monsanto process having Rhodium based catalyst
i.e. [Rh(CO)2I2]–

CO  CH 3OH  Rh
 CH 3COOH
47. The process is based on an iridium-containing catalyst, such as the complex [Ir(CO2I2]–.
The catalyst is more robust (strong) at extremely low water concentration as against required for the Rh catalyst.
48. The process is faster and more effective with iridium, iodide, requiring a smaller amount of catalyst.
Iridium is even more selective for methanol, increases the overall yield and reduces byproducts, resulting in lower
purification costs and reduced waste.
49. (a), (b), (c), (d) all are correct.
50. In Wacker’s process, ethylene is converted into acetaldehyde by a combination of palladium and copper, or, to
vinyl acetate in the presence of acetic acid.
1 [PdCl4 ]
CH2 = CH2 + O2 
Catalyst  CH 3CHO
2 acetaldehyde

51. Rh(I)  4d8

PPh3  strong field ligand  low spin
hybridisation  dsp2
magnetic moment  diamagnetic in nature
Geometry  square planar.
Ph3P PPh3
Rh
Cl PPh3

16 e diamagnetic
52. Homogeneous catalyst retains the characteristic reactivity pattern that is showed as a homogeneous catalyst.
– Properties of homogeneous catalyst are usually distinct from those of classical heterogeneous catalyst.
53.  used for the hydrogenation of alkenes and alkynes.
54. TEC = 1 + 9 + 2 + 3 × 2 = 18e–.
55. 65%(n) : 35%(i)
1.85 : 1
i.e.  1.9 : 1
Amount of reactant (in mole)
56. TON   % yield of product
Amount of catalyst (in moles)

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QUANTA POINT Sol-(10) /Catalysis
0.138
TON   0.35 [1 millimole = 0.001M]
2.75  10 –3
0.138
  0.35  17.56
0.00275
0.138M
57. TON   0.5  25.09
0.00275M
25.09
TOF   1.39 / h
18

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Sol- (11) Metallocenes
HINTS & SOLUTION
1. In case of d5 metallocenes there is crossing of orbitals and picture of FMO’s become like this
e1
e2
a1
2. In case of d5 metallocenes there is crossing of orbitals and picture of FMO’s become like this
e1
e2
a1
3. PhCH2 attack benzene ring as ene are more reactive than enyls.
4. Mechanism

Cl AlCl3 CH2
CH2 Cl CH 2
Fe + Cp CH 2
(1)

Cl
CH2 CH 2

(2) Fe anhy. AlCl 3

+ H 2C CH2Cl Fe
AlCl 3 removes Cl–

CH2 CH 2 CH3
Fe
1, 2
Fe Fe Fe
Fe H-Shif t Cp

5. Ferrocene has 18 valence electrons and the protonation at the Fe centre does not change the total valence
electrons in the product. NiCp2 has 20e and if the same mechanism occurs, then the hypothetical [NiCp2H]+
would still be a 20e species. However, if the protonation occurs directly at Cp ring, the product [NiCp(4 –
C5H6)]+ attains the 18e configuration. The reaction is more facile in the Ni complex because of the driving force
to attain the 18e product.

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6. HNO3 acts as oxidising agent.
7. I2 acts as oxidising agent.
8. FeCl3 acts as oxidising agent.

Ni
Triple deckers
9.
Ni

10. (I) Ferrocene is diamagnetic (II) Dipole moment is zero

(IV) Kealy and Pauson synthesised ferrocene from C5H5MgBr and FeCl3.
11. Co(C5H5)2  19e– paramagnetic species gets oxidised easily and therefore it is an air sensitive.

12. Electronic configuration of Cp2CO is given below. On oxidation the electron is removed from antibonding orbital.
 M – C bond length decreases.
e*1
a1

e2

13. Nickelocene is 20e– species gets substituted by NO to form 18e– complex.

U 2– Ligand  [C 8H8]2–

2– Formal charge  2–
14. on ligand
U 4+
8

2–

15. Electron count of linear NO = 3

Electron count of bent NO = 1
 Sum = 4
16. Electronic configuration of MnCp2 in solid state
e1
a1

e2

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Sol- (12) Spectra Fluxonality
HINTS & SOLUTION
1. In option ‘b’ the TEC is
8+2×3+5–1
8+6+4
 18e–

Br — Br
2. Fe 2 (CO) 4 (Cp) 2 Na Fe Fe
Ti
OC OC Br
CO CO
H H
 5– M
all 5H = 1 signal
5 H H
H
Fe Hc Hc H a – 1 signal
OC 1  1– 2Hb – 1 signal
CO
Hb Hb 2Hc – 1 signal
(B)
M
Ha
PPh3
PR3 CO
3. Fe(CO) 5 + NaBH4 [HFe(CO)4] – OC Fe
BuOH
(X) CO
PPh3
(Y)

Cl CN
NaCN
4. [Cr(CO)6] + Cl Cr Cr
OC CO CO OC CO CO
5. [Ru(PPh3)2(NO)2Cl]+
8 + 2 × 2 + x + y + 1 – 1 = 16
x + y = 16 – 12 = 4

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QUANTA POINT Sol-(12) /Spectra Fluxonality
x + y = 4  One NO is linear & one NO is bent.
 Both have different length but there is little difference due to back bonding.
6. Linear NO is NO+ which donates electron from sigma bonding filled molecular orbital and accepts electron in its
pi star. Whereas bent NO is NO– which only does sigma donation from its pi star to the d orbital of metal.
7. Electron count = 7 + 4 × 2 + 3 = 18
Due to presence of strong field ligands all the electrons are paired.
8. [Ru(PPh3)2(NO)2Cl]
8 + 2 × 2 + x + y + 1 – 1 = 16  x + y = 4
This shows one NO  linear
One NO  bent
9. ‘a, b, c’ all are correct.
10. a, b, c all are correct
11. Correct options are (a, b, c)
12. Cp* become more electron rich due to which -back bonding increase and vCO decreases.
Correct options are (b, c)
13. General formula for C3V symmetry is (n – 1)
 (n – 1) = (3 – 1)
= 2 bands.
Correct answer is (2)

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Sol- (13) Coupling
HINTS & SOLUTION
1. Mizoroki reaction – Vinyl
Negishi coupling – Zn
Miyaura coupling – Borane
Hiyama coupling – Organosilane
Correct option is (c)
OTf CO2Et
CO2Et
2. + Bu3Sn
NHAc NHAc
3. The correct sequence for the mechanism of Kumada coupling will be
Ox
ad idati
dit ve
ion
min on
n
atio
Eli ducti
Re

s
an ion
Tr llat
e ta
m
Correct option is (b)

TfO Cl + (OH)2B TfO

4.
Me Me
5. The correct sequence will be oxidative addition.
Ox
ad idati
dit ve
ion
min on
n
atio
Eli ducti
Re

on
dati
ll a
a
bop
r
Ca
Correct option is (a)

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QUANTA POINT Sol-(13) /Coupling

Cl OTHP OTHP
+H Pd(PPh3)4 H SiMe3
6.
Cl OTHP CuI
B4NH2 Cl
(A) SiMe3
(B)
The above example is of sonogashira coupling.
Me
I Me
CO2Me
7. N N

SO2Ph SO2Ph
The above reaction is heck coupling
8. The rate of transmetalation will be alkynyl > alkenyl > aryl > allyl > > alkyl
9. When Pd catalyst is used, order of reactivity of halides is I > Br > Cl
and when Ni catalyst is used  Cl > I > Br

N Br
10. MgBr N
S S S S
11. Miyaura coupling can be used for the synthesis poly-olefins, styrenes, substituted biphenyls.
Correct option is (d)
12. Buchwald-Hartwig coupling involves the coupling of an aryl halide with an amine in the presecne of base such as
NaOtBu to form aromatic amines i.e. to form C – N bonds.
Correct option is (c)
13. Palladium catalyzed intramolecular cross coupling using distannanes is called Stille-Kelly coupling
14. The Hiyama coupling involves the cross coupling between alleyl, alkeyl or aryl halides with organometallics in the
presence of the Pd catalysts.
Correct option is (b)
15. Kumuda coupling or Kumuda-Corriu coupling was the first Pd or Ni catalyzed cross coupling.
Correct option is (b)
16. All statements are correct
17. This reaction does not requires a base.
18. Cu(I) is used as a Co-Catalyst.
19. Except Heck coupling all other involve transmetalation in their mechanism.

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