Sorbonne Université, CNRS, Laboratoire de Chimie Théorique, UMR 7616, 75005, Paris, France.
Institut Charles Gerhardt, UMR 5253 CNRS-UM2-UM1-ENSCM 8, rue de l'Ecole Normale, 34296, Montpellier Cedex 5, France.
Chemistry. 2018 May 2;24(25):6617-6624. doi: 10.1002/chem.201800099. Epub 2018 Apr 14.
Exchange of X (F, Cl, OMe) and a substituted enolate chain between SiMe and various Cu complexes was examined. Reaction mechanisms pass through a cyclic transition state in which the reaction coordinate is associated with rotation of the SiMe 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.
研究了 SiMe 和各种 Cu 配合物之间的 X（F、Cl、OMe）交换和取代烯醇盐链的交换。反应机理经过一个环状过渡态，其中反应坐标与 SiMe 部分的旋转相关。考察了热力学和动力学特征对活性和辅助配体性质的依赖性。当使用稳定的烯醇盐时，形成铜烯醇盐被证明是有利的。用 Cl 取代 F 会改变反应的偏好。这与 Cu-Cl 和 Si-Cl 键能之间的微小差异有关，而其他 Si-X 键则比它们的 Cu-X 类似物系统地更强。
