Oxidative‐Insertion Reactivity Across a Geometrically Constrained Metal→Borane Interaction. Issue 25 (11th May 2017)

• Record Type: Journal Article
• Authors: Barnett, Brandon R.; Neville, Michael L.; Moore, Curtis E.; Rheingold, Arnold L.; Figueroa, Joshua S.
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 25(2017)
• Page Start: 7195
• Page End: 7199
• Publication Date: 2017-05-11
• Subjects: boranes -- cooperative effects -- insertion -- platinum -- structure elucidation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201702151
• Languages: English
• ISSNs: 1433-7851

Abstract

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(κ 2 ‐N, B‐ Cy2 BIM)(CNAr Dipp2 )] 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. Abstract : A'B'ru'Pt' activation : Known cooperative bond activations across metal→borane bonds have been essentially limited to oxidative addition‐type reactions. The singly buttressed platinum→borane complex [Pt(κ 2 ‐ N, B ‐ Cy2 BIM)(CNAr Dipp2 )] 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.