Carbon-Nitrogen Bond Cleavage by a Thorium-NHC-bpy Complex

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• 作者：Mary E. Garner ; Dr. Stephan Hohloch ; Prof. Dr. Laurent Maron and Prof. Dr. John Arnold
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：October 24, 2016
• 年：2016
• 卷：55
• 期：44
• 页码：13789-13792
• 全文大小：1216K
• ISSN：1521-3773

文摘

Actinide complexes demonstrate unparalleled reactivity towards small molecules. However, utilizing these powerful transformations in a predictable and deliberate manner remains challenging. Therefore, developing actinide systems that not only perform noteworthy chemistry but also demonstrate controllable reactivity is a key goal. We describe a bis(NHC)borate thorium-bpy complex (1) that is capable of reductively cleaving the R−NC bond in a series of organic isocyanides. In contrast to most actinide-mediated bond activations, the dealkylation event mediated by 1 is remarkably general and yields very well-defined products that assist in mechanistic elucidation. Synthesis of the rearranged but-3-enyl product from the reaction of 1 and cyclopropylmethyl isocyanide supports the notion of a radical-based mechanism.