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Carbon–Nitrogen Bond Cleavage by a Thorium‐NHC‐bpy Complex
Author(s) -
Garner Mary E.,
Hohloch Stephan,
Maron Laurent,
Arnold John
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201607899
Subject(s) - reactivity (psychology) , isocyanide , chemistry , actinide , bond cleavage , molecule , combinatorial chemistry , thorium , photochemistry , computational chemistry , organic chemistry , inorganic chemistry , catalysis , materials science , medicine , alternative medicine , uranium , pathology , metallurgy
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.