title: A silyliumylidene cation stabilized by an amidinate ligand and 4-dimethylaminopyridine.
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.
authors.affiliation: Division of Chemistry and Biological Chemistry, Nanyang Technological University, 21 Nanyang Link, Singapore 637371.
authors.forename: Hui-Xian
authors.initials: HX
authors.lastname: Yeong
authors.forename: Hong-Wei
authors.initials: HW
authors.lastname: Xi
authors.forename: Yongxin
authors.initials: Y
authors.lastname: Li
authors.forename: Kok Hwa
authors.initials: KH
authors.lastname: Lim
authors.forename: Cheuk-Wai
authors.initials: CW
authors.lastname: So
keywords: N ligands; carbene homologues; cations; density functional calculations; silicon