Kinetics and mechanism of the oxidative addition of methyl iodide to [Rh(CH3COCHCOCF3)(CO)(P(OCH2)3CCH3)]: an experimental and computational study

Experimental and density functional theory results of the oxidative addition and CO insertion steps of methyl iodide with [Rh(CH 3 COCHCOCF 3 )(CO)(P(OCH 2 ) 3 CCH 3 )] are presented. Large negative experimental values for the activation entropy and results from a density functional theory study ind...

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Bibliographic Details
Published in:Reaction kinetics, mechanisms and catalysis mechanisms and catalysis, 2012-04, Vol.105 (2), p.233-247
Main Authors: Erasmus, Johannes J. C., Conradie, Marrigje M., Conradie, Jeanet
Format: Article
Language:English
Subjects:
Catalysis
Chemistry
Chemistry and Materials Science
Industrial Chemistry/Chemical Engineering
Physical Chemistry
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Summary:Experimental and density functional theory results of the oxidative addition and CO insertion steps of methyl iodide with [Rh(CH 3 COCHCOCF 3 )(CO)(P(OCH 2 ) 3 CCH 3 )] are presented. Large negative experimental values for the activation entropy and results from a density functional theory study indicated trans addition of the CH 3 I to [Rh(CH 3 COCHCOCF 3 )(CO)(P(OCH 2 ) 3 CCH 3 )]. Although the electron withdrawing CF 3 group slows down the oxidative addition step, the strong electron donation of P(OCH 2 ) 3 CCH 3 still accelerates the oxidation addition step by ca 20 times (at 35 °C) compared to that of the Monsanto catalyst.
ISSN:1878-5190
1878-5204
DOI:10.1007/s11144-011-0413-1