Colebatch Annie L, Hawkey Gilder Benjamin W, Whittell George R, Oldroyd Nicola L, Manners Ian, Weller Andrew S
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, UK.
School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
Chemistry. 2018 Apr 11;24(21):5450-5455. doi: 10.1002/chem.201800737. Epub 2018 Mar 23.
The rhodium complex [Rh(Ph PCH CH CH PPh )(η -FC H )][BAr ], 2, catalyzes BH/BD exchange between D and the boranes H B⋅NMe , H B⋅SMe and HBpin, facilitating the expedient isolation of a variety of deuterated analogues in high isotopic purities, and in particular the isotopologues of N-methylamine-borane: R B⋅NMeR 1-d (R=H, D; x=0, 2, 3 or 5). It also acts to catalyze the dehydropolymerization of 1-d to give deuterated polyaminoboranes. Mechanistic studies suggest a metal-based polymerization involving an unusual hybrid coordination insertion chain-growth/step-growth mechanism.
铑配合物[Rh(Ph₂PCH₂CH₂CH₂PPh₂)(η⁶-FC₆H₅)][BArF₄], 2, 催化D与硼烷H₃B⋅NMe₃、H₃B⋅SMe₂和HBpin之间的BH/BD交换，有助于快速分离出各种高同位素纯度的氘代类似物，特别是N-甲胺硼烷的同位素异构体：R₃B⋅NMe₃⁻d (R = H, D; x = 0, 2, 3或5)。它还能催化1-d的脱氢聚合反应，生成氘代聚氨基硼烷。机理研究表明，这是一种基于金属的聚合反应，涉及一种不寻常的混合配位插入链增长/逐步增长机理。
