A silyliumylidene cation stabilized by an amidinate ligand and 4-dimethylaminopyridine.

TitleA silyliumylidene cation stabilized by an amidinate ligand and 4-dimethylaminopyridine.
Publication TypeJournal Article
Year of Publication2013
AuthorsYeong H-X, Xi H-W, Li Y, Lim KH, So C-W
JournalChemistry (Weinheim an der Bergstrasse, Germany)
Volume19
Issue35
Pagination11786-90
Date Published2013 Aug 26
Abstract

The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4-dimethylaminopyridine (DMAP) are described. The reaction of the amidinate silicon(I) dimer [LSi:]2 (1; L = PhC(NtBu)2) with one equivalent of N-trimethylsilyl-4-dimethylaminopyridinium triflate [4-NMe2C5H4NSiMe3]OTf and two equivalents of DMAP in THF afforded [LSi(DMAP)]OTf (2). The ambiphilic character of 2 is demonstrated from its reactivity. Treatment of 2 with 1 in THF afforded the disilylenylsilylium triflate [L'2(L)Si]OTf (3; L' = LSi:) with the displacement of DMAP. The reaction of 2 with [K{HB(iBu)3}] and elemental sulfur in THF afforded the silylsilylene [LSiSi(H){(NtBu)2C(H)Ph}] (4) and the base-stabilized silanethionium triflate [LSi(S)DMAP]OTf (5), respectively. Compounds 2, 3, and 5 have been characterized by X-ray crystallography.

DOI10.1002/asia.201300600
Alternate JournalChemistry