Abstract
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)][BArF 4], 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 language | English |
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Pages (from-to) | 1481-1495 |
Number of pages | 15 |
Journal | Journal of the American Chemical Society |
Volume | 140 |
Issue number | 4 |
Early online date | 29 Dec 2017 |
DOIs | |
Publication status | Published - 31 Jan 2018 |
ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
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Profiles
-
Stuart Alan Macgregor
- School of Engineering & Physical Sciences, Institute of Chemical Sciences - Professor
- School of Engineering & Physical Sciences - Professor
Person: Academic (Research & Teaching)