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

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

doi:10.1021/acscatal.0c02211

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

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

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	7443-7448
Number of pages	6
Journal	ACS Catalysis
Volume	10
Issue number	14
Early online date	17 Jun 2020
DOIs	https://doi.org/10.1021/acscatal.0c02211 https://doi.org/10.1021/acscatal.0c02211
Publication status	Published - 17 Jul 2020

Bibliographical note

Keywords

amine-borane
dehydropolymerization
mechanism
phosphine
rhodium

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Cite this

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

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.",

keywords = "amine-borane, dehydropolymerization, mechanism, phosphine, rhodium",

author = "Ryan, {David E.} and Andrea, {Kori A.} and Race, {James J.} and Boyd, {Timothy M.} and Lloyd-Jones, {Guy C.} and Weller, {Andrew S.}",

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T2 - Resting State, Chain Control, and Efficient Polymer Synthesis

AU - Ryan, David E.

AU - Andrea, Kori A.

AU - Race, James J.

AU - Boyd, Timothy M.

AU - Lloyd-Jones, Guy C.

AU - Weller, Andrew S.

PY - 2020/7/17

Y1 - 2020/7/17

N2 - 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.

AB - 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.

KW - amine-borane

KW - dehydropolymerization

KW - mechanism

KW - phosphine

KW - rhodium

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JF - ACS Catalysis

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ER -

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

Abstract

Bibliographical note

Keywords

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Putting Low Coordination into Practice by the Exploration of Metal-sigma-Interactions: Fundamentals, New Catalysts and Catalysis for New Materials

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

Abstract

Bibliographical note

Keywords

Access to Document

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Putting Low Coordination into Practice by the Exploration of Metal-sigma-Interactions: Fundamentals, New Catalysts and Catalysis for New Materials

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