Read e-book online Aspects of Homogeneous Catalysis: A Series of Advances PDF

By R. S. Coffey (auth.), Renato Ugo (eds.)

ISBN-10: 9401033412

ISBN-13: 9789401033411

ISBN-10: 9401033439

ISBN-13: 9789401033435

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Extra info for Aspects of Homogeneous Catalysis: A Series of Advances Volume 1

Example text

Min-I [139]. The rate is too fast to measure accurately and other factors prevent good kinetic data being obtained in this particular system. The complex has a low solubility, is slow to dissolve, and gives deeply coloured solutions making it difficult to prepare true homogeneous solutions. In addition the solution is very sensitive to minute traces of oxygen and peroxides and this increases the difficulty of obtaining reproducible results. Furthermore the catalyst dies off during hydrogenation.

Previously RhCl(PHPh2)a had been prepared from [RhCl(C2H4)2]2 via reaction (42) [82] and various phosphite analogues RhX(P(OR)s)a had been known a long time [83]. Refiuxing an ethanolic solution of RhC1a3H20 with six molar equivalents of triphenylphosphine gives RhCl(PPhs)s in almost quantitative yield (18], the phosphine being the reducing agent (18, 79]. The corresponding bromide and iodide can be prepared similarly using the appropriate rhodium halide [77] or from RhC1a3H20 and an excess of lithium halide (18].

Rate in cc. 1. 1 MECHANISM OF HYDROGENATION AND HYDROGEN DEUTERIUM EXCHANGE The properties of RhHCO(pPha)a and the kinetics of hydrogenation indicate that hydrogenations proceed via scheme 2 [125]. " k"/7 /:" // ~ HaRhCOP2 Scheme 2 fast 42 under mild conditions as coordination of olefin would give a seven co-ordinate intermediate or direct formation of an alkyl. ~~~--~ KI is the equilibrium constant shown in scheme 2 and [] denotes a concentration. It is assumed all other reactions in scheme 2 are rapid.

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Aspects of Homogeneous Catalysis: A Series of Advances Volume 1 by R. S. Coffey (auth.), Renato Ugo (eds.)


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