二氯硅烯亲合性的调控：二氯硅烯-氮杂环卡宾配合物ClSi-IPr的亲核行为

Tuning Philicity of Dichlorosilylene: Nucleophilic Behavior of the Dichlorosilylene-NHC Complex ClSi-IPr.

作者信息

Lee Vladimir Ya, Horiguchi Satoru, Sekiguchi Akira, Gapurenko Olga A, Gribanova Tatyana N, Minkin Vladimir I, Gornitzka Heinz

机构信息

Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.

Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachki Avenue, Rostov on Don 344090, Russian Federation.

出版信息

ACS Omega. 2019 Feb 8;4(2):2902-2906. doi: 10.1021/acsomega.8b03429. eCollection 2019 Feb 28.

DOI:10.1021/acsomega.8b03429

PMID:31459520

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6648269/

Abstract

Novel unsaturated four-membered ring disilene, 3,3-dichloro-1,2,4,4-tetrakis[di--butyl(methyl)silyl]-Δ-1,2,3,4-trisilagermetene, was synthesized by the ring expansion reaction of the three-membered ring 1-disilagermirene with the silylene-NHC complex ClSi-IPr. The mechanism of the unexpected formation of this compound was verified by high-level density functional theory computations, which revealed n-π as the dominant orbital interaction.

摘要

新型不饱和四元环二硅烯，3,3 - 二氯 - 1,2,4,4 - 四[二 - 丁基（甲基）甲硅烷基] - Δ - 1,2,3,4 - 三硅锗烯，通过三元环1 - 二硅锗烯与硅烯 - NHC配合物ClSi - IPr的扩环反应合成。通过高水平密度泛函理论计算验证了该化合物意外形成的机理，结果表明n - π为主要的轨道相互作用。