Affiliation:
1. 1University of the Free State
Abstract
AbstractThe reaction rate of the oxidative addition and CO insertion steps of methyl iodide with [Rh(PhCOCHCOPh)(CO)(P(OCH2)3CCH3)] are presented. Large negative experimental values for the activation entropy and results from a density functional theory computational chemistry study indicated trans addition of the CH3I to [Rh(PhCOCHCOPh)(CO)(P(OCH2)3CCH3)]. A study of the molecular orbitals gives insight into the flow of electrons during the oxidative addition reaction. CO insertion leads to a square pyramidal [Rh(PhCOCHCOPh)(P(OCH2)3CCH3)(COCH3)(I)] acyl product with the COCH3 moiety in the apical position. The strong electron donation of the P(OCH2)3CCH3 ligand accelerates the oxidation addition step of methyl iodide to [Rh(PhCOCHCOPh)(CO)(P(OCH2)3CCH3)] by ca. 265 times faster (at 35°C) than that of the Monsanto catalyst, but inhibits the CO insertion step.
Subject
Materials Chemistry,General Chemistry
Reference56 articles.
1. J.P. Collman, L.S. Hegedus, J.R. Norton, R.G. Finke, Principles and Applications of Organotransition Metal Chemistry (University Science Books, California, 1987)
2. A. Haynes, B.E. Mann, P.M. Maitlis, J. Am. Chem. Soc. 115, 4093 (1993)
3. L. Cavallo, M. Sola, J. Am. Chem. Soc. 123, 12294 (2001)
4. A. Haynes, P.M. Maitlis, G.E. Morris, G.J. Sunley, H. Adams, P.W. Badger, C.M. Bowers, D.B. Cook, P.I.P. Elliot, T. Ghaffer, H. Green, T.R. Griffin, M. Payne, J.M. Pearson, M.J. Taylor, P.W. Vickers, R. Watt, J. Am. Chem. Soc. 126, 2847 (2007)
5. E. Mieczynska, A.M. Trzeciak, J.J. Ziólkowski, J. Mol. Catal. 80, 189 (1993)
Cited by
5 articles.
订阅此论文施引文献
订阅此论文施引文献，注册后可以免费订阅5篇论文的施引文献，订阅后可以查看论文全部施引文献