Ryan, David E., Andrea, Kori A., Race, James J. et al. (3 more authors) (2020) Amine-Borane Dehydropolymerization Using Rh-Based Precatalysts : Resting State, Chain Control, and Efficient Polymer Synthesis. ACS Catalysis. pp. 7443-7448. ISSN 2155-5435
Abstract
A detailed study of H3B·NMeH2 dehydropolymerization using the cationic pre-catalyst [Rh(DPEphos)(H2BNMe3(CH2)2tBu)]-[BArF4], identifies the resting state as dimeric [Rh(DPEphos)H2]2 and boronium [H2B(NMeH2)2]+ as the chain-control agent. [Rh(DPEphos)H2]2 can be generated in situ from Rh(DPEphos)(benzyl), and catalyzes polyaminoborane formation (H2BNMeH)n [Mn = 15000 g mol–1]. Closely-related Rh(Xantphos)(benzyl) operates at 0.1 mol%, to give higher molecular weight polymer [Mn = 85000 g mol–1] on gram scale with low residual [Rh], 81 ppm. This insight offers a mechanistic template for dehydropolymerization.
Metadata
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Copyright, Publisher and Additional Information: | © 2020 American Chemical Society | ||||
Keywords: | amine-borane, dehydropolymerization, mechanism, phosphine, rhodium | ||||
Dates: |
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Institution: | The University of York | ||||
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) | ||||
Funding Information: |
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Depositing User: | Pure (York) | ||||
Date Deposited: | 18 Jun 2020 08:20 | ||||
Last Modified: | 06 Dec 2023 13:43 | ||||
Published Version: | https://doi.org/10.1021/acscatal.0c02211 | ||||
Status: | Published | ||||
Refereed: | Yes | ||||
Identification Number: | https://doi.org/10.1021/acscatal.0c02211 | ||||
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