1428342-10-2Relevant academic research and scientific papers
A stable singlet biradicaloid siladicarbene: (L:)2Si
Mondal, Kartik Chandra,Roesky, Herbert W.,Schwarzer, Martin C.,Frenking, Gernot,Niep?tter, Benedikt,Wolf, Hilke,Herbst-Irmer, Regine,Stalke, Dietmar
, p. 2963 - 2967 (2013)
A trapped silicon atom: The compound (L:)2Si with low-valent silicon was synthesized from its dichloride biradical precursor (L:) 2SiCl2 by reduction with KC8. Theoretical analysis suggest that there are two donor-acceptor σ bonds L:→Si←:L. There is one σ lone-pair orbital at Si and one π orbital which features significant π-back-donation L:←Si→:L giving short Si-C bonds. Copyright
Trapping a Silicon(I) Radical with Carbenes: A Cationic cAAC–Silicon(I) Radical and an NHC–Parent-Silyliumylidene Cation
Li, Yan,Chan, Yuk-Chi,Leong, Bi-Xiang,Li, Yongxin,Richards, Emma,Purushothaman, Indu,De, Susmita,Parameswaran, Pattiyil,So, Cheuk-Wai
, p. 7573 - 7578 (2017)
The trapping of a silicon(I) radical with N-heterocyclic carbenes is described. The reaction of the cyclic (alkyl)(amino) carbene [cAACMe] (cAACMe=:C(CMe2)2(CH2)NAr, Ar=2,6-iPr2C6H3) with H2SiI2 in a 3:1 molar ratio in DME afforded a mixture of the separated ion pair [(cAACMe)2Si:.]+I? (1), which features a cationic cAAC–silicon(I) radical, and [cAACMe?H]+I?. In addition, the reaction of the NHC–iodosilicon(I) dimer [IAr(I)Si:]2 (IAr=:C{N(Ar)CH}2) with 4 equiv of IMe (:C{N(Me)CMe}2), which proceeded through the formation of a silicon(I) radical intermediate, afforded [(IMe)2SiH]+I? (2) comprising the first NHC–parent-silyliumylidene cation. Its further reaction with fluorobenzene afforded the CAr?H bond activation product [1-F-2-IMe-C6H4]+I? (3). The isolation of 2 and 3 confirmed the reaction mechanism for the formation of 1. Compounds 1–3 were analyzed by EPR and NMR spectroscopy, DFT calculations, and X-ray crystallography.
