Tuning Philicity of Dichlorosilylene: Nucleophilic Behavior of the Dichlorosilylene-NHC Complex Cl2Si-IPr

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

doi:10.1021/acsomega.8b03429

Tuning Philicity of Dichlorosilylene: Nucleophilic Behavior of the Dichlorosilylene-NHC Complex Cl₂Si-IPr

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

Authors

Vladimir Ya Lee¹, Satoru Horiguchi¹, Akira Sekiguchi¹, Olga A Gapurenko², Tatyana N Gribanova², Vladimir I Minkin², Heinz Gornitzka³

Affiliations

¹ Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.
² Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachki Avenue, Rostov on Don 344090, Russian Federation.
³ CNRS, LCC, Université de Toulouse, UPS, INPT, 205 Route de Narbonne, BP 44099, Toulouse Cedex 4 F-31077, France.

Abstract

Novel unsaturated four-membered ring disilene, 3,3-dichloro-1,2,4,4-tetrakis[di-tert-butyl(methyl)silyl]-¹Δ-1,2,3,4-trisilagermetene, was synthesized by the ring expansion reaction of the three-membered ring 1-disilagermirene with the silylene-NHC complex Cl₂Si-IPr. The mechanism of the unexpected formation of this compound was verified by high-level density functional theory computations, which revealed n_Si:(HOMO)-π_Si=Si(LUMO) ^* as the dominant orbital interaction.