A Disilene Base Adduct with a Dative Si-Si Single Bond

Abstract

An experimental and theoretical study of the base-stabilized disilene 1 is reported, which forms at low temperatures in the disproportionation reaction of Si2 Cl6 or neo-Si5 Cl12 with equimolar amounts of NMe2 Et. Single-crystal X-ray diffraction and quantum-chemical bonding analysis disclose an unprecedented structure in silicon chemistry featuring a dative Si→Si single bond between two silylene moieties, Me2 EtN→SiCl2 →Si(SiCl3 )2 . The central ambiphilic SiCl2 group is linked by dative bonds to the amine donor and the bis(trichlorosilyl)silylene acceptor, which leads to push-pull stabilization. Based on experimental and theoretical examinations a formation mechanism is presented that involves an autocatalytic reaction of the intermediately formed anion Si(SiCl3 )3 (-) with neo-Si5 Cl12 to yield 1.

Keywords: X-ray diffraction; bonding analysis; dative bonds; disilenes; silylenes.