CEM-203:Organometallic Chemistry-I

1. Explain ‘reversal of polarity’ during the reaction of transition metal bound alkene complexes.

2. Arrange the following compounds in the increasing order of ethylene C-C bond length

3. Which of the following metal alkene complex do you think will look most like a metalla cyclopropane?
Explain your answer. (i) (CH2=CH2)Ni(PPh3)2 (ii) (CH2=CH2)Fe(CO)4

4. If an olefin has to bind to a transition metal, which of the olefins, cis-cyclooctene or trans-cyclooctene
will form the stronger complex and why?

5. Schematically present the possible orbital interaction in Fischer’s and Schrock’s complexes. Discuss on
the magnetic behavior in each case.

6. Using the given carbonyl stretching frequencies, compare the electronic properties of the carbene
with the carbyne.

7. Write the structures of the species A-D in following reactions

8. Draw the probable binding modes of allyl ligand.

9. Consider the 18 electron rule as a guide and determine the value of ‘n ‘ in the following complexes

(a) Na2Fe(CO)n (b) MnBr(CO)n (c) W(6-C6H6)(CO)n (d) Rh(5-C5H5)(CO)n (e) Cr(3-C5H5)(CO)n(CH3)
10. Determine the number of M-M bonds in the following complexes

(a) [(CO)2Rh(-Cl)2Rh(CO)2] (b) [(5-C5H5)(CO)Fe(-CO)2Fe(CO)(5-C5H5)]

11. Discuss the NMR of the following fluxional molecules

(a) [Fe2(CO)4(5-C5H5)2 (b) Fe(CO)3(C8H8)

12. What is ‘Tebbe’s reagent’? How will you synthesize this reagent? Write down the course of the
reaction when Tebbe’s reagent is treated with a ketone RR’(C=O) in pyridine. Mention the final product.

13. Justify the 1,2-migration mechanism in the ‘ring wizzing’ of 1-Cp in [Fe(5-Cp)(1-Cp)(CO)2] with
respect to NMR spectroscopy.

14. Discuss the phenomenon of ‘carbonyl scrambling’ in *FeCp(CO)2]2 complex.

15. What are Fischer type and Schrock type carbenes. Give two examples of each. How Fischer type
carbene differs from Schrock type carbene?

16. Write down the product(s) of treatment of [Cr(CO)6] with LiCH3 followed by [(CH3)3O]BF4. Propose
the mechanism.

17. What is the fundamental difference between the alkene and alkyne complexes while binding to the
transition metal ion? Draw the possible binding modes of alkyne to transition metal ions.

18. How cyclohexyne can be stabilized by reacting with Pt(PPh3)3 in presence of Na/Hg? Write down the
reaction with structure of the complex.

19. Which among the following alkenes will bind most strongly to a metal? Give reasons

(i) Cyclooctadiene (ii) ethylene (iii) norborene (iv) cyclohexene

20. Discuss the phenomenon of metallacycle formation in transition metal alkene complex with a
suitable example.

21. ’Beryllocene is highly fluxional’ justify the statement.

22. “IR spectroscopy of olefin complexes is a less useful probe of -bonding than IR spectroscopy of CO
–complexes”- Justify.

23. The Pt-C and C-C bond length data are given for complex 1 and 2.

dC-C (Å) dPt-c (Å)

Pt(Ph3P)2(2-C2H4) (1) 1.43 2.11
Pt(Ph3P)2(2-C2(CN)4) (2) 1.49 2.11

Draw the structure of complex 1 and 2 and discuss their bonding

24. ‘NMR Spectroscopy is applied to detect/monitor stereochemical non-rigidity’ Justify

25. Discuss the binding modes of ‘alkene’ ligand in ‘transition metal alkene’ complexes. 2

26.

‘In the above reaction, the attack of hydride ion at on 2-coordinated alkyne can lead to 3-allyl
complex.’ Suggest the mechanism of this transformation.

27. Write down the complete reaction when Mo(CO)6 is refluxed with norboranediene in octane media.

28. Predict the product of the following reactions