A General, Rhodium‐Catalyzed, Synthesis of Deuterated Boranes and N‐Methyl Polyaminoboranes. Issue 21 (23rd March 2018) - Colebatch, Annie L.
Abstract: The rhodium complex [Rh(Ph2 PCH2 CH2 CH2 PPh2 )(η 6 ‐FC6 H5 )][BAr F 4 ], 2, catalyzes BH/BD exchange between D2 and the boranes H3 B⋅NMe3, H3 B⋅SMe2 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: R3 B⋅NMeR2 1‐ d x (R=H, D; x= 0, 2, 3 or 5). It also acts to catalyze the dehydropolymerization of1‐ d x to give deuterated polyaminoboranes. Mechanistic studies suggest a metal‐based polymerization involving an unusual hybrid coordination insertion chain‐growth/step‐growth mechanism. Abstract : Deuterated amine‐boranes, prepared in high isotopic purities and yields, can be dehydropolymerized to give deuterated polyaminoboranes; for which mechanistic studies suggest an unusual hybrid coordination insertion chain‐growth/step‐growth mechanism.