5 years ago

Oxidative-Insertion Reactivity Across a Geometrically Constrained MetalBorane Interaction

Oxidative-Insertion Reactivity Across a Geometrically Constrained MetalBorane Interaction
Arnold L. Rheingold, Joshua S. Figueroa, Brandon R. Barnett, Michael L. Neville, Curtis E. Moore
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., MBR3) remains limited. Described herein is that the platinum (boryl)iminomethane (BIM) complex [Pt(κ2-N,B-Cy2BIM)(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. A'B'ru'Pt' activation: Known cooperative bond activations across metalborane bonds have been essentially limited to oxidative addition-type reactions. The singly buttressed platinumborane complex [Pt(κ2-N,B-Cy2BIM)(CNArDipp2)] can effect either the 1,1- or 1,2-insertion of various organic and inorganic substrates. Further, insertion can be coupled with subsequent C−N bond formation to effect release of functionalized substrate.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201702151

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