| dc.contributor.author | Erasmus, Johannes J. C. | |
| dc.contributor.author | Conradie, Jeanet | |
| dc.date.accessioned | 2022-06-29T06:31:32Z | |
| dc.date.available | 2022-06-29T06:31:32Z | |
| dc.date.issued | 2011-11-24 | |
| dc.description.abstract | The reaction rate of the oxidative addition and CO insertion steps of methyl iodide with [Rh(PhCOCHCOPh)(CO)(P(OCH<sub>2</sub>
)
<sub>3</sub>
CCH<sub>3</sub>
)]
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 CH<sub>3</sub>
I to [Rh(PhCOCHCOPh)(CO)(P(OCH<sub>2</sub>
)
<sub>3</sub>
CCH<sub>3</sub>
)]. 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(OCH<sub>2</sub>
)
<sub>3</sub>
CCH<sub>3</sub>
)(COCH<sub>3</sub>
)(I)] acyl product with the COCH<sub>3</sub>
moiety in the apical position. The strong electron donation of the P(OCH<sub>2</sub>
)
<sub>3</sub>
CCH<sub>3</sub>
ligand accelerates the oxidation addition step of methyl iodide to [Rh(PhCOCHCOPh)(CO)(P(OCH<sub>2</sub>
)
<sub>3</sub>
CCH<sub>3</sub>
)] by ca. 265 times faster
(at 35°C) than that of the Monsanto catalyst, but inhibits the CO insertion step. | en_US |
| dc.identifier.citation | Erasmus JJC, Conradie J. Oxidative addition of methyl iodide to [Rh(PhCOCHCOPh)(CO)(P(OCH2)(3)CCH3)]: an experimental and computational study. Central European Journal of Chemistry. 2012;10(1):256-266 | en_US |
| dc.identifier.cristinID | FRIDAID 919265 | |
| dc.identifier.doi | 10.2478/s11532-011-0137-0 | |
| dc.identifier.issn | 1895-1066 | |
| dc.identifier.issn | 1644-3624 | |
| dc.identifier.uri | https://hdl.handle.net/10037/25635 | |
| dc.language.iso | eng | en_US |
| dc.publisher | De Gruyter | en_US |
| dc.relation.journal | Central European Journal of Chemistry | |
| dc.rights.accessRights | openAccess | en_US |
| dc.rights.holder | Copyright 2011 The Author(s) | en_US |
| dc.title | Oxidative addition of methyl iodide to [Rh(PhCOCHCOPh)(CO)(P(OCH2)(3)CCH3)]: an experimental and computational study | en_US |
| dc.type.version | publishedVersion | en_US |
| dc.type | Journal article | en_US |
| dc.type | Tidsskriftartikkel | en_US |
| dc.type | Peer reviewed | en_US |
English
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