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A Highly Active PBP–Iridium Catalyst for the Dehydrogenation of Dimethylamine–Borane: Catalytic Performance and Mechanism
Author(s) -
Kwan Enrique Huang,
Ogawa Hayato,
Yamashita Makoto
Publication year - 2017
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201700384
Subject(s) - dimethylamine , dehydrogenation , borane , catalysis , iridium , chemistry , ammonia borane , catalytic cycle , medicinal chemistry , ligand (biochemistry) , pincer ligand , rhodium , polymer chemistry , photochemistry , pincer movement , organic chemistry , biochemistry , receptor
A long‐tethered boron‐containing (P‐B‐P) pincer ligand with an aliphatic backbone was synthesized. Oxidative addition of the B−H bond in the ligand to [Ir(coe) 2 Cl] 2 (coe=cyclooctene) afforded the (P‐B‐P)Ir(H)Cl complex. A catalyst system comprising the iridium complex and KO t Bu showed excellent performance in the dehydrocoupling of N , N ‐dimethylamine–borane (DMAB), releasing 1 equivalent of dihydrogen gas from a concentrated solution of DMAB at a low catalyst loading of 0.05 mol % and with an initial turnover frequency of approximately 3400 h −1 . The dihydride (P‐B‐P)Ir(H) 2 complex also catalyzed the dehydrogenation of DMAB and was postulated as one of the intermediates in the catalytic cycle.