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

Gemma M. Adams, Annie L. Colebatch, Joseph T. Skornia, Alasdair I. McKay, Heather C. Johnson, Guy C. Lloyd-Jones, Stuart A. Macgregor, Nicholas A. Beattie, Andrew S. Weller*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


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)21-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, D = 1.9) promotes significantly higher degrees of polymerization than cationic 6 (Mn = 9000 g mol-1, D = 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.

Original languageEnglish
Pages (from-to)1481-1495
Number of pages15
JournalJournal of the American Chemical Society
Issue number4
Publication statusPublished - 31 Jan 2018


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