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Amine-Borane Dehydropolymerization Using Rh-Based Precatalysts: Resting State, Chain Control, and Efficient Polymer Synthesis

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Author(s)

  • David E. Ryan
  • Kori A. Andrea
  • James J. Race
  • Timothy M. Boyd
  • Guy C. Lloyd-Jones
  • Andrew S. Weller

Department/unit(s)

Publication details

JournalACS Catalysis
DateAccepted/In press - 15 Jun 2020
DateE-pub ahead of print - 17 Jun 2020
DatePublished (current) - 17 Jul 2020
Issue number14
Volume10
Number of pages6
Pages (from-to)7443-7448
Early online date17/06/20
Original languageEnglish

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.

Bibliographical note

© 2020 American Chemical Society

    Research areas

  • amine-borane, dehydropolymerization, mechanism, phosphine, rhodium

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