Enabling and Probing Oxidative Addition and Reductive Elimination at a Group 14 Metal Center: Cleavage and Functionalization of E–H Bonds by a Bis(boryl)stannylene

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• 作者：Andrey V. Protchenko ; Joshua I. Bates ; Liban M. A. Saleh ; Matthew P. Blake ; Andrew D. Schwarz ; Eugene L. Kolychev ; Amber L. Thompson ; Cameron Jones ; Philip Mountford ; Simon Aldridge
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：April 6, 2016
• 年：2016
• 卷：138
• 期：13
• 页码：4555-4564
• 全文大小：481K
• ISSN：1520-5126

文摘

By employing strongly σ-donating boryl ancillary ligands, the oxidative addition of H₂ to a single site Sn^II system has been achieved for the first time, generating (boryl)₂SnH₂. Similar chemistry can also be achieved for protic and hydridic E–H bonds (N–H/O–H, Si–H/B–H, respectively). In the case of ammonia (and water, albeit more slowly), E–H oxidative addition can be shown to be followed by reductive elimination to give an N- (or O-)borylated product. Thus, in stoichiometric fashion, redox-based bond cleavage/formation is demonstrated for a single main group metal center at room temperature. From a mechanistic viewpoint, a two-step coordination/proton transfer process for N–H activation is shown to be viable through the isolation of species of the types Sn(boryl)₂·NH₃ and [Sn(boryl)₂(NH₂)]⁻ and their onward conversion to the formal oxidative addition product Sn(boryl)₂(H)(NH₂).