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Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7195-7199. doi: 10.1002/anie.201702151. Epub 2017 May 11.

Oxidative-Insertion Reactivity Across a Geometrically Constrained Metal→Borane Interaction.

Author information

1
Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC 0358, La Jolla, CA, 92193, USA.

Abstract

While interest in cooperative reactivity of transition metals and Lewis acids is receiving significant attention, the scope of known reactions that directly exploit the polarized reverse-dative σ-bond of metal-borane complexes (i.e., M→BR3 ) remains limited. Described herein is that the platinum (boryl)iminomethane (BIM) complex [Pt(κ2 -N,B-Cy2 BIM)(CNArDipp2 )] can effect the oxidative insertion of a range of unsaturated organic substrates, including azides, isocyantes, and nitriles, as well as CO2 and elemental sulfur (S8 ). In addition, alkyl migration processes available to the BIM framework allow for post-insertion reaction sequences resulting in product release from the metal center.

KEYWORDS:

boranes; cooperative effects; insertion; platinum; structure elucidation

PMID:
28493627
DOI:
10.1002/anie.201702151

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