Oxidative addition of methyl iodide to [Rh(PhCOCHCOPh)(CO)(P(OCH2)3CCH3)]: an experimental and computational study

• Authors: Johannes Erasmus , Jeanet Conradie
• Languages of publication: EN

Abstracts

EN

The 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.

Keywords

EN

Benzoylacetone; Rhodium; Oxidative addition; Phosphite; DFT

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2012
• Volume: 10
• Issue: 1
• Pages: 256-266

Dates

published

1 - 2 - 2012

online

24 - 11 - 2011

Contributors

author

Johannes Erasmus

• University of the Free State

author

Jeanet Conradie

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Identifiers

DOI

10.2478/s11532-011-0137-0