Reaction Kinetics, Mechanisms and Catalysis
Volume/Issue:
Volume 105: Issue 2
Kinetics and mechanism of the oxidative addition of methyl iodide to [Rh(CH3COCHCOCF3)(CO)(P(OCH2)3CCH3)]: an experimental and computational study
Authors: Johannes J. C. Erasmus 1 , Marrigje M. Conradie 1 , 2 , and Jeanet Conradie 1 , 2
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  • 1 Department of Chemistry, University of the Free State, PO Box 339, Bloemfontein 9300, Republic of South Africa
  • 2 Department of Chemistry and Centre for Theoretical and Computational Chemistry, University of Tromso, 9037, Troms⊘, Norway
DOI:
https://doi.org/10.1007/s11144-011-0413-1
Page Count:
233–247
Publication Date:
01 Apr 2012
Online Publication Date:
27 Dec 2011
Article Category:
Research Article
Restricted access

Abstract

Experimental and density functional theory results of the oxidative addition and CO insertion steps of methyl iodide with [Rh(CH3COCHCOCF3)(CO)(P(OCH2)3CCH3)] are presented. Large negative experimental values for the activation entropy and results from a density functional theory study indicated trans addition of the CH3I to [Rh(CH3COCHCOCF3)(CO)(P(OCH2)3CCH3)]. Although the electron withdrawing CF3 group slows down the oxidative addition step, the strong electron donation of P(OCH2)3CCH3 still accelerates the oxidation addition step by ca 20 times (at 35 °C) compared to that of the Monsanto catalyst.

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Cover Reaction Kinetics, Mechanisms and Catalysis
Reaction Kinetics, Mechanisms and Catalysis
Print ISSN:
1878-5190
Online ISSN:
1878-5204
Keywords:
Rhodium; Oxidative addition; Phosphate; DFT; β-Diketone

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