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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 and So, Cheuk-Wai 2017. Trapping a silicon(I) radical with carbenes: a cationic cAAC-silicon(I) radical and an NHC-parent-silyliumylidene cation. Angewandte Chemie 129 (26) , pp. 7681-7686. 10.1002/ange.201702760

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Abstract

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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: Wiley-VCH Verlag
ISSN: 0044-8249
Date of First Compliant Deposit: 16 June 2017
Date of Acceptance: 24 May 2017
Last Modified: 30 Jun 2019 05:29
URI: http://orca.cf.ac.uk/id/eprint/101507

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