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CSIR-UGC-NET/JRF | GATE CHEMISTRY

TEST : ORGANOMETALLIC COMPOUNDS

Time 00 : 45 Hour Date : 31-10-2017

M.M. : 60
INSTRUCTION :
1. There are Two Parts. Part-A contains 10 objective type questions, each question carry 2 marks and
Part-B contains 10 objective type questions, each question carry 4 marks.
2. There is negative marking, @ 25% will be deducted for each wrong answer.
3. Attempt all the questions, use of calculator is not allowed.

PART - A

5  103 1 
1. The carbonyl resonance in 13C NMR spectrum of  CpRh  CO    Rh, I  , 100%  .
3  2 
Shows a triplet at –65C owing to the presence of
(a) Terminal CO (b) µ2  CO (c) µ3  CO (d) 5Cp

h
2. Cr  CO 6  NO   P Cr  NO  x 
The complex ‘P’ is homoleptic complex and follows 18 electron the value of ‘x’ will be
(a) 3 (b) 4 (c) 0 (d) 5
2 6
3. The cluster Co 6  CO 15  ,  Fe5  CO 15 C  and  Ni5  CO 10  having the structure respectively..
(a) closo, arachno, nido (b) nido, arachno, closo
(c) closo, nido, arachno (d) closo, closo, nido
4. For complex (A) to follow 18 electron rule missing ligand should be
Me Me
P
Mo (A)
P C
Me Me C
CH3

(a) 6  C 7 H 8 (b) 8  C8 H 8 (c) 7  C 7 H 7 (d) 4  C 4 H 4

5. Arrange the following in order of their increasing  M C stretching frequency

2  
(A)  Hf  CO 6  (B) Ta  CO 6  (C)  W  CO 6  (D)  Re  CO  6 
2 3
(E) Os  CO 6  (F)  Ir  CO 6 
(a) A < B < C < D < E < F (b) F < E < D < C < B < A
(c) A < B < C < E < D < F (d) F < E < D < C < A < B

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6. In the complex Me4Al2(µ-Me)2, the two alkyl acts as a bridging ligands. This seems to happens by 2e, three
centre bond involving between metal and alkyl carbon. The hapticity of terminal and bridging alkyl groups are
respectively.
(a) 1 , 2 (b) 2 , 1 (c) 3 , 1 (d) 1 , 1
7. Consider the metal carbonyl complex (A)
q
 M  CO  6  where q = –2, –1, 0, +1
The strongest  C–O band in IR spectrum can be observed when the value of q will be
(a) –2 (b) –1 (c) 0 (d) +1
2
8.  Ru 6  CO 18  is isolobal with
2 4 2
(a)  B6 H6  (b)  B5H5  (c) Ir4  CO 12 (d)  Fe 4  CO 13 

9. Suggest what changes in cluster structure might accompany the reaction:

 
Co 6  CO 15 N  
 Co6  CO 13 N   2CO
(a) Octahedron to trigonal prism (b) Square pyramid to trigonal bipyramid
(c) Tetrahedron to octahedron (d) Trigonal prism to octahedron

10. [Ph3C]BF4
–Ph3CH
BF4
Mo
Mo OC CO
OC CO CO
CO

The oxidation state of Mo in the reactant and product are respectively

(a) 0, 1 (b) 1, 1 (c) 0, 0 (d) 2, 0

PART-B

11. 5 CpFe  CO   (A) is a dark green solid compound. The IR spectrum shows a single CO stretching band
4

at 1640 cm . The 1H NMR spectrum shows a single line even at low temperature. Which of the following
–1

statement is not true on the basis of gien data about the structure of  CpFe  CO   4
5

(a) The complex (A) follows the 18 electron rule.

(b) The total number of M–M bonds in complex are six.
(c) All CO’s are present 3 -mode.
(d) Two CO’s are present in µ2-mode where as another two CO’s are present at µ3 modes.

12. Which of the following Molybdenum complex having highest  CO carbonyl stretching frequency
(a)  Mo  CO 3  PF3 3  (b)  Mo  CO 3  PCl3 3 

(c)  Mo  CO 3  PClPh 2 3  (d)  Mo  CO 3  PMe3 3 

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13. Match List-A (organometallic compound) with List-B (1H NMR chemical-shift for marked proton)
List-A List-B
(A) Mn  CO 5 H (I) 10.22 ppm

(B) Ni    C2 H 4 3
2
(II) 3.06 ppm

(C)    C6 H 6  2 Cr
6
(III) –7.5 ppm
CH3
(D) (5–C 5H5)2 Ta CH2 (IV) 4.12 ppm
–
(a) A-III, B-IV, C-II, D-I (b) A-III, B-II, C-IV, D-I
(c) A-I, B-II, C-III, D-IV (d) A-II, B-III, C-I, D-IV
14. The cluster having arachno type structure is
2
(a)  Ir4  CO 12  (b)  Rh 6  CO 16  (c) Os6  CO 18  (d)  Ru 5C  CO 16 

15. A compound A having the composition FeC9 H8O3 shows one signal at 2.5 ppm and another one around 5.0
ppm in its 1H NMR spectrum. The IR spectrum of this compound shows two bands around 1900 and 1680
cm–1. The compound follows the 18 electron rule of the following statements for A, the correct one is/are
(A) It has 5  Cp group. (B) It has a terminal CO ligand.
(C) It has a CH3 ligand (D) It has Fe–H bond.
(a) (A) and (B) only (b) (C) only (c) (A) and (C) only (d) (B) and (D) only.
16. Complexes of general formula, fac-[Mo(CO)3(phosphine)3] have the C—O stretching bands as given below.
Phosphines: PF3(A); PCl3(B); P(Cl)Ph2(C); PMe3(D)
v(CO), cm–1: 2090(i); 2040(ii); 1977(iii); 1945(iv)
The correct comibination of the phsphine and the streching frequency is,
(a) (A–i), (B–ii), (C–iii), (D–iv) (b) (A–ii), (B–i), (C–iv), (D–iii)
(c) (A–iv), (B–iii), (C–ii), (D–i) (d) (A–iii), (B–iv), (C–i), (D–ii)
17. Find the best possible combination of metal ligand and charge. So, that the complex (X) follows 18 electron
rule.
z
M  L 
 x
(a) M  Co, L  CO, x  4, z  3 (b) M  Fe, L  CN , x  4, z  2
(c) M  Fe, L  CO, x  4, z  2 (d) M  Mn, L  PPh3 , x  5, z  2
18. Ti4+ seldom forms stable carbonyl complexes because
(a) Antibonding orbitals of CO    are high in energy..
*

(b) CO increases electron density on the metal Ti4+

(c) The d set of metal  t 2 g  orbtal find no match with the CO   
(d) Absence of back bonding as the metal present in highest oxidation state.

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19. Indenyl is a well know organometallic ligand the structure of indenyl ligand is the haptacity and

electron contribution for the indenyl complex [(Indenyl)Fe(Cp)(CO)2] are respectively.

(a) 1, 1 (b) 3, 1 (c) 1, 3 (d) 1, 0
20. Which of the following complex does not obey 18 electron rule.

 2

(a)  W  CO 3   H 2 P Pr3 2 
i
  
(b) OsH 2  H 2 P  OEt 3 
 4

O

OC C CO
OC Cl CO
OC Fe Fe CO
(c) (d) Rh Rh
H
OC CO OC Cl CO
C
O

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North Delhi : 33-35, Mall Road, G.T.B. Nagar (Opp. Metro Gate No. 3), Delhi-09, Ph: 011-65462244, 65662255
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CSIR-UGC-NET/JRF | GATE CHEMISTRY Date : 31-10-2017

TEST : ORGANOMETALLIC COMPOUNDS

[ANSWERS]

PART-A

1. (b) 2. (b) 3. (c) 4. (c) 5. (b) 6. (d) 7. (d)

8. (a) 9. (d) 10. (c)

PART-B

11. (d) 12. (a) 13. (b) 14. (d) 15. (a) 16. (a) 17. (c)
18. (d) 19. (a) 20. (d)

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North Delhi : 33-35, Mall Road, G.T.B. Nagar (Opp. Metro Gate No. 3), Delhi-09, Ph: 011-65462244, 65662255