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A Silyliumylidene Cation Stabilized by an Amidinate Ligand and 4‐Dimethylaminopyridine
Author(s) -
Yeong HuiXian,
Xi HongWei,
Li Yongxin,
Lim Kok Hwa,
So CheukWai
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201300255
Subject(s) - trifluoromethanesulfonate , chemistry , trimethylsilyl , ligand (biochemistry) , reactivity (psychology) , medicinal chemistry , dimer , trimethylsilyl trifluoromethanesulfonate , stereochemistry , catalysis , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology
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 [ L Si:] 2 ( 1 ; L =PhC(N t Bu) 2 ) with one equivalent of N ‐trimethylsilyl‐4‐dimethylaminopyridinium triflate [4‐NMe 2 C 5 H 4 NSiMe 3 ]OTf and two equivalents of DMAP in THF afforded [ L Si(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′ = L Si:) with the displacement of DMAP. The reaction of 2 with [K{HB( i Bu) 3 }] and elemental sulfur in THF afforded the silylsilylene [ L SiSi(H){(N t Bu) 2 C(H)Ph}] ( 4 ) and the base‐stabilized silanethionium triflate [ L Si(S)DMAP]OTf ( 5 ), respectively. Compounds 2 , 3 , and 5 have been characterized by X‐ray crystallography.