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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 International Edition 56 (26) , pp. 7573-7578. 10.1002/anie.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
ISSN: 1433-7851
Last Modified: 05 Nov 2019 03:25
URI: http://orca-mwe.cf.ac.uk/id/eprint/123525

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