_P.-Powell-auth.-Principles-of-Organometallic-Chemistry-Springer-Netherlands-1988

Problems
FISCHER-TROPSCH
Henrici-Olive, G. and Olive. S. ( 1984) The Chemistry of the Catalyzed Hydrogenation of Carbon
Monoxide, Springer Verlag, Berlin.
Herrmann, W.A. (1982) Angew. Chem. (Int. Edn). 21. 117.
SYN.GAS
Forster. D. (1979) Adv. Organomet. Chem., 17. 255.
King, D.L. and Grate, J.H. (1985) Chem. Tech., 244.
Maugh, T.H .. II (1983) Science, 220, 1032.
SUPPORTED METAL CATALYSTS
Bailey, D.C. and Langer, S.H. (1981) Chem. Revs., 81. 109.
Problems
1. 'The activity of a catalytic process is the major criterion for its large scale
industrial application.' Discuss this statement and illustrate with examples from
homogeneously catalysed processes.
(Royal Holloway College and Bedford College).
2. 'Homogeneous catalysis mediated by complexes of transition elements
relies primarily on the ability of such complexes to undergo oxidative
addition/reductive elimination reactions.'
Propose suitable mechanisms for the following processes:
NiHCl(C0) 2
(a) RC-CH + CO + MeOH ------->
R
HC=C/
2
'-COOMe
Fe(COI,
(b) l, 5-cyclooctadiene ___ _, l. 3-cyclooctadiene
(Heriot-Watt University)
3. Complexes ofthe type Ni{P(OR) 3 } 4 catalyse the isomerization of but-l-ene to
cis- and trans-but-2-ene in benzene solution in the presence of CF ,C0 2 H. Propose
a cycle for this process, discussing the important steps.
(University of Southampton).
4. Both the selectivity and the activity of rhodium systems which catalyse
alkene hydroformylation are improved by the addition of PPh 3 • However. the
rhodium complex so formed. [HRh(C0) 2 (PPh,)J. does not catalyse alkene
isomerization.
By considering the mechanism of the hydroformylation reaction, account for
these observations.
(University of Southampton).
397