Mechanism of Enolate Transfer between Si and Cu
In: ISSN: 0947-6539, 2018
academicJournal
Zugriff:
International audience ; Exchange of X (F, Cl, OMe) and a substituted enolate chain between SiMe3 and various CuI complexes was examined. Reaction mechanisms pass through a cyclic transition state in which the reaction coordinate is associated with rotation of the SiMe3 moiety. The dependence of the thermodynamic and kinetic features on the nature of the active and ancillary ligands was examined. Formation of copper enolate is shown to be favored when stabilized enolates are used. Replacement of F by Cl reverses the preference of the reaction. This is associated with the small difference between the Cu−Cl and Si−Cl bond energies, in contrast to other Si−X bonds, which are systematically stronger than their Cu−X analogues.
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Mechanism of Enolate Transfer between Si and Cu
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Autor/in / Beteiligte Person: | Bouaouli, Samira ; Spielmann, Kim ; Vrancken, Emmanuel ; Campagne, Jean-Marc ; Gérard, Hélène ; Laboratoire de chimie théorique (LCT) ; Institut de Chimie - CNRS Chimie (INC-CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS) ; Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM) ; Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS) ; ANR-09-BLAN-0089,CopEnol,Caractérisation et Propriétés d'Enolates de Cuivre Conjugués(2009) |
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Zeitschrift: | ISSN: 0947-6539, 2018 |
Veröffentlichung: | HAL CCSD ; Wiley-VCH Verlag, 2018 |
Medientyp: | academicJournal |
DOI: | 10.1002/chem.201800099 |
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