Dehydropolymerization of H3B·NMeH2 To Form Polyaminoboranes Using [Rh(Xantphos-alkyl)] Catalysts

A systematic study of the catalyst structure and overall charge for the dehydropolymerization of H3B·NMeH2 to form N-methyl polyaminoborane is reported using catalysts based upon neutral and cationic {Rh­(Xantphos-R)} fragments in which PR2 groups are selected from Et, iPr, and tBu. The most efficient systems are based upon {Rh­(Xantphos-iPr)}, i.e., [Rh­(κ3-P,O,P-Xantphos-iPr)­(H)2(η1-H3B·NMe3)]­[BArF4], 6, and Rh­(κ3-P,O,P-Xantphos-iPr)­H, 11. While H2 evolution kinetics show both are fast catalysts (ToF ≈ 1500 h–1) and polymer growth kinetics for dehydropolymerization suggest a classical chain growth process for both, neutral 11 (Mn = 28 000 g mol–1, Đ = 1.9) promotes significantly higher degrees of polymerization than cationic 6 (Mn = 9000 g mol–1, Đ = 2.9). For 6 isotopic labeling studies suggest a rate-determining NH activation, while speciation studies, coupled with DFT calculations, show the formation of a dimetalloborylene [{Rh­(κ3-P,O,P-Xantphos-iPr)}2B]+ as the, likely dormant, end product of catalysis. A dual mechanism is proposed for dehydropolymerization in which neutral hydrides (formed by hydride transfer in cationic 6 to form a boronium coproduct) are the active catalysts for dehydrogenation to form aminoborane. Contemporaneous chain-growth polymer propagation is suggested to occur on a separate metal center via head-to-tail end chain B–N bond formation of the aminoborane monomer, templated by an aminoborohydride motif on the metal.