单体锂和钠硅基苯甲基配合物的合成、结构和 C-O 键烯烃化反应。

Monomeric lithium and sodium silylbenzyl complexes: syntheses, structures, and CO bond olefination.

机构信息

Chemistry-School of Natural and Environmental Sciences, Newcastle University, Newcastle upon Tyne NE1 7RU, UK.

出版信息

Chem Commun (Camb). 2023 Jun 27;59(52):8083-8086. doi: 10.1039/d3cc01376f.

PMID:37291981

Abstract

Herein we report the syntheses, structures and reactivity studies of two new monomeric alkali metal silylbenzyl complexes stabilised by a tetradentate amine ligand, tris[2-(dimethylamino)ethyl]amine (MeTren). The two complexes, namely [MR'(MeTren)] (R': CH(Ph)(SiMe)) (2-Li: M = Li; 2-Na: M = Na), exhibit significant different coordination modes according to their metal identity (Li: σ-coordination; Na: π-coordination). Reactivity studies of 2-Li and 2-Na reveal that they are efficient in promoting a widely-used class of organic functional group interconversion: CO bond olefination of ketones, aldehydes and amides, to produce tri-substituted internal alkenes.

摘要

在此，我们报告了两种新的单核碱金属硅基苄基配合物的合成、结构和反应性研究，这些配合物由四齿胺配体三[2-(二甲氨基)乙基]胺(MeTren)稳定。这两个配合物，即[MR'(MeTren)]（R'：CH(Ph)(SiMe)）（2-Li：M = Li；2-Na：M = Na），根据其金属种类表现出明显不同的配位模式（Li：σ-配位；Na：π-配位）。2-Li 和 2-Na 的反应性研究表明，它们能够有效地促进一类广泛使用的有机官能团转化：酮、醛和酰胺的 C-O 键烯烃化，生成三取代的内烯烃。