QUESTION BANK- ORGANOMETALLICS

Definition, classification, hapticity

1. Define an organometallic compound. Which of the following are organometallic compounds?
Give reasons.
(i) CH3MgBr
(ii) (C2H5)4Zn
(iii) Ti(OEt)4
(iv) Ti(CH3)(OEt)3
(v) B(OMe)3
(vi) (5-C5H5)2Fe
(vii) K[PtCl3(C2H4)]
(viii) (6-C6H6)2Cr

2. What is meant by the term hapticity? Give an example where the same ligand can show varying
hapticity.
3. How are organometallic compounds classified on the basis of bonding? Give an example of
each type.
Carbonyls, 18 electron rule, Zeise’s salt
4. Using the MO diagram of CO explain
(i) CO acts as an electron pair donor and acceptor through carbon and not through
oxygen and formation of both sigma and π bond involve carbon.
(ii) CO has negligible donor properties to Lewis acids like BF3 but binds to transition
metals
(iii) CO is referred to as a π acid ligand.
5. What is synergic effect? How does it account for the formation of carbonyls with transition
metals in low oxidation states?
6. Ni forms a mononuclear carbonyl but the cobalt carbonyl is dimeric. Explain.
7. What is meant by π acidity? Is CO a stronger π acid ligand than NO+or not? Justify your choice.
8. Account for the following:
(i) Manganese does not form a stable mononuclear carbonyl.
(ii) Iron forms a pentacarbonyl but nickel forms a tetracarbonyl.
(iii) The V – C bond lengths in V(CO)6 and V(CO)6- are different.
 (iv) All Ni – C bond lengths in Ni(CO)4 are identical but Fe – C bond lengths in Fe(CO)5
are not identical.
(v) The carbonyls of 4d metals are less stable than the corresponding carbonyls of 3d
metals
(vi) Despite being a 17 electron species V(CO)6 does not dimerise
(vii) N2 is isoelectronic with CO, but dinitrogen complexes are less common than
carbonyl complexes.

9. Will the C- O bond length in metal carbonyls be longer or shorter than that in CO? Justify
your answer.

10. Why is the 18 electron rule for the 3d metals followed in the middle of the series?

11. How does the total valence electron count of the central metal atom in carbonyls and their
derivatives reflect their stability? Predict which of the following will be stable:
(a) V(CO)5NO (b) Cr(C6H6)(CO)3 (c) V(CO)6 (d) Co(CO)4
(e) Mn(CO)5Br (f) [Co(CO)4]-
12. Using the 18 electron rule as a guide find/ identify:
(i) the number of CO ligands in [Fe(NO)2(CO)n ,
[V(NO)(CO)n], [W(ƞ -C6H6)(CO)n] , [Co(ƞ5-C5H5)(CO)n]
6

(ii) the number of metal – metal bonds in Fe3(CO)12 , Co4(CO)12

(iii) the 3d metal in [M(CO)6]- , [M(CO)4]2 ,
[M(CO)5]2 , M2(CO)9 [M(ƞ5C5H5)(CO)3] [(6-C6H6)M(C2H4)2]
(iv) the charge on the species [Co(CO)4]x , [Fe(CO)4]x
(v) the number of ligands m and n in [(6-C6H6)nCr(CO)m]

13. The mononuclear carbonyl of iron has a trigonal bipyramidal structure which can be
verified by IR spectral analysis showing two sets of carbonyls – axial and equatorial. The
X ray pattern indicates two different Fe -C bond lengths. However, the NMR spectrum of
the same compound shows only one kind of carbonyl group and identical Fe – C bond
lengths. Discuss.

14. Draw the structures of the following compounds:

(a) Co2(CO)8 in solid state (b) Co2 (CO)8 in hexane (c) Fe3 (CO)12
(d) Fe2 (CO)9

15. The ʋC-O values in [Fe(CO)4]2- , [Co(CO)4]- and Ni(CO)4 are 1788, 1918 and 2121cm-1
respectively while the ʋC-O value for CO(g) is 2143cm-1. Explain the trend.
16. The CO stretching frequency in IR spectra are as follows: [Mn(CO)6]+ 2090 cm-1, Cr(CO)6
2000 cm-1, [V(CO)6]- 1860, [Ti(CO)6]2- 1750 cm-1. The value for CO (g) is 2143 cm-1.
Discuss.

17. Fe(CO)5 is known while [Fe(CO)6] is not. Why?

18. Arrange the following species in increasing order of the property mentioned and give
reason:
(i) [Mn(CO)6]2+, [Cr(CO)6]+, V(CO)6 – IR stretching frequency of C – O bond
(ii) [Ti(CO)6]2- , Cr(CO)6 - IR stretching frequency of C – O bond
(iii) Ni(CO)4 , [Co(CO)4]- - C – O bond length
(iv) Fe(CO)5, [Fe(CO)4] 2-
- Fe – C bond order
(v) Terminal CO, bridging CO - C – O bond order

19. Which is more basic towards a proton and why – [Mn(CO)5]-, [Re(CO)5]- ?
20. Which is a more powerful nucleophile and why – [Mn(CO)5]-, [Co(CO)4]- ?

21. Give any 2 methods of preparation of metal carbonyls. What happens when Fe(CO)5 reacts
with bromine?

22. Give the valence electron counts of the metal in the following:
[Mn2(CO)10], [V(CO)5 (NO)], [Fe(π C5H5)(CO], [Fe2(CO)9] [Mn(π
C5H5)(CO)2]

23. Explain the changes observed in the IR stretching frequency of the C –O bond in (i)
terminal and bridging carbonyl group, (ii) in carbonyl compounds of the same metal when
some CO molecules are replaced by poor π acceptor groups?

24. Predict whether the following obey the EAN rule:

[Mn(C2H4)(CO)5]+, [Co(π-C3H5)(CO)3], Cr(CO)6, [V(CO)6]¯,
25. Two different structures of Co2(CO)8 are consistent with 18 electron rule. How will you
predict the structure on the basis of IR studies?
26. Using VBT derive the structures of ; Cr(CO)6, Fe(CO)5, Ni(CO)4, Mn2(CO)10.

27. What is meant by synergic effect? How does it account for the formation of carbonyl
complexes of transition metals in low oxidation states? Does the synergic effect also play
a role in strengthening platinum-carbon bond in Zeise’s salt?
28. How do you rationalize the increase in the C-C bond length from 133.7 pm in ethene to
137.5 pm in Zeise’s salt, accompanied by a decrease in C-C stretching frequency from
1623 cm-1 to 1526 cm-1?
 29. Draw the structure of the anion of Zeise’s salt and briefly discuss the nature of bonding.
Give 2 evidences to indicate that back bonding occurs in this compound
.
Alkyls
30. Draw the structure of methyl lithium. In which category of organometallic compounds will
you place it? What are the coordination numbers of Li and C in the tetramer?
31. Both AlEt3 and AlCl3 dimerize but the nature of alkyl bridging and halide bridging in the
dimers are different. Justify.
32. Draw the structure of dimeric trialkyl aluminium and explain why all Al – C bond lengths
are not identical.

Ferrocene
33. The cyclopentadienyl rings in ferrocene have aromatic charcter but cyclopentadiene itself
has no such character. Explain.
34. Give two methods of synthesis of ferrocene and discuss its structures in solid and gaseous
states.
35. Give two reactions of ferrocene which show it is more reactive than benzene.
36. Ferrocene on acetylation with excess of reagent shows heteroannular substitution while on
alkylation with excess of reagent shows hemoannular substitution. Give reason.
37. Explain why direct nitration of ferrocene is not possible? How can you get nitro derivative
of ferrocene?
38. Give two reactions each to highlight similarities and differences between ferrocene and
benzene.
39. Which is more stable and why: [Fe(ƞ5-C5H5)2] or [Co(ƞ5-C5H5)2]?
40. How will you prepare aminoferrocene from ferrocene?

1 Mark Questions

1. Is the given compound an organometallic compound? (1mark for each choice)

(a) CH3MgBr
(b) Zn(C2H5)2
 (c) Ti(OEt)4
(d) Ti(CH3)(OEt)3
(e) B(OMe)3
(f) (5-C5H5)2Fe
(g) K[PtCl3(C2H4)]
(h) (6-C6H6)2Cr
(i) Mn(CN)2
(j) Si(CH3)2Cl2
(k) Pb(Et)4
(l) Sn(EtNH2)2
2. Give one example of each of the following: (1 mark for each option)
(a) Ionic organometallic compound
(b) Sigma bonded covalent organometallic compound
(c) Non classically bonded organometallic compound
(d) Organometallic compound with bridging alkyl group
(e) π complex
3. What type of bonding is present in lithium alkyl?
4. In which category of organometallic compounds will you place ferrocene?
5. Apart from CO give an example of a π – acid ligand.
6. Through which atom does CO act as an electron pair donor?
7. Through which atom does CO act as an electron pair acceptor?
8. Why is CO a π acid ligand?
9. Why does Ni form a tetracarbonyl?
10. The tetracarbonyl of iron is not known, comment.
11. Why is V(CO)6 less stable than [V(CO)6]-?
12. Which is more stable V(CO)6 or V(CO)5(NO)?
13. Which is more stable Cr(CO)6 or W(CO)6
14. Give an example of a mononuclear carbonyl which is thermally unstable.
15. Give an example of synthesis of a metal carbonyl by direct combination.
16. Give the valence electron count of the metal in:
(a) [Mn2(CO)10],
(b) [Fe(π C5H5)(CO],
(c) [Fe2(CO)9]
(d) [Mn(π C5H5)(CO)2]
(e) [Cr(ƞ6-C6H6)(CO)3]
(f) Na[Co(CO)4]
(g) K2[Fe(CO)4]
(h) [Mn(CO)5]Br
17. Is the IR stretching frequency of CO of a bridging carbonyl higher or lower than that of a
terminal carbonyl?
18. Questions 18,19 and 20 of the previous set without reason, only choice of compound
19. How will the carbon – carbon bond length be affected if the hydrogen atoms of ethene in
Zeise’s salt are replaced by fluorine?
20. Which is the most stable metallocene?
21. What is the product obtained when ferrocene is treated with:
(a) Acetyl chloride in excess in presence of aluminium chloride
(b) Alkyl halide in excess in presence of aluminium chloride
(c) Dimethylamine and formaldehyde
(d) n-butyl lithium
22. How is nitroferrocene prepared from ferrocene?
23. Give one reaction to highlight similarity of ferrocene and benzene.
24. Give one reaction to show that ferrocene is more reactive than benzene.