Spontaneous trans‐Selective Transfer Hydrogenation of Apolar Boron–Boron Double Bonds. Issue 29 (6th June 2019)

• Record Type: Journal Article
• Authors: Dömling, Michael; Arrowsmith, Merle; Schmidt, Uwe; Werner, Luis; Castro, Abril C.; Jiménez‐Halla, J. Oscar C.; Bertermann, Rüdiger; Müssig, Jonas; Prieschl, Dominic; Braunschweig, Holger
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 29(2019)
• Page Start: 9782
• Page End: 9786
• Publication Date: 2019-06-06
• Subjects: amine borane dehydrocoupling -- DFT mechanism -- diboranes -- diborene -- transfer hydrogenation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201902656
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The transfer hydrogenation of N‐heterocyclic carbene (NHC)‐supported diborenes with dimethylamine borane proceeds with high selectivity for the trans ‐1, 2‐dihydrodiboranes. DFT calculations, supported by kinetic studies and deuteration experiments, suggest a stepwise proton‐first‐hydride‐second reaction mechanism via an intermediate μ‐hydrodiboronium dimethylaminoborate ion pair. Abstract : Game of borons : The transfer hydrogenation of apolar cis ‐ and trans ‐diborenes with dimethylamine borane as the hydrogen source proceeds with high selectivity for the corresponding trans ‐1, 2‐dihydrodiboranes. DFT calculations, supported by kinetic data, reveal a new reaction mechanism proceeding via a proton‐first‐hydride‐second pathway through an intermediate μ‐hydrodiboronium aminoborate ion pair.