The simplest amino‐borane H2B=NH2 trapped on a rhodium dimer: pre‐catalysts for amine–borane dehydropolymerization

Amit Kumar; Nicholas Beatie; Sebastian A Pike; Stuart A. Macgregor; Andrew S Weller

doi:10.1002/anie.201600898

The simplest amino‐borane H₂B=NH₂ trapped on a rhodium dimer: pre‐catalysts for amine–borane dehydropolymerization

Amit Kumar, Nicholas Beatie, Sebastian A Pike, Stuart A. Macgregor, Andrew S Weller

School of Chemistry

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

51 Citations (Scopus)

Abstract

The μ‐amino–borane complexes [Rh₂(L^R)₂(μ‐H)(μ‐H₂B=NHR′)][BAr^F₄] (L^R=R₂P(CH₂)₃PR₂; R=Ph, ⁱPr; R′=H, Me) form by addition of H₃B⋅NMeR′H₂ to [Rh(L^R)(η⁶‐C₆H₅F)][BAr^F₄]. DFT calculations demonstrate that the amino–borane interacts with the Rh centers through strong Rh‐H and Rh‐B interactions. Mechanistic investigations show that these dimers can form by a boronium‐mediated route, and are pre‐catalysts for amine‐borane dehydropolymerization, suggesting a possible role for bimetallic motifs in catalysis

Original language	English
Pages (from-to)	6651-6656
Journal	Angewandte Chemie International Edition
Volume	55
Issue number	23
Early online date	21 Apr 2016
DOIs	https://doi.org/10.1002/anie.201600898
Publication status	Published - 27 May 2016

Keywords

Amino-borane
Dehydrocoupling
DFT
Catalytic mechanisms
Rhodium dimers

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10.1002/anie.201600898Licence: CC BY

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Copyright © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 1.9 MBLicence: CC BY

Amit Kumar
- ak336st-andrews.acuk
- School of Chemistry - Principal Research Fellow
Person: Academic - Research

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@article{d9e28ab17e9949a6990a6f93def9cfd1,

title = "The simplest amino‐borane H2B=NH2 trapped on a rhodium dimer: pre‐catalysts for amine–borane dehydropolymerization ",

abstract = "The μ‐amino–borane complexes [Rh2(LR)2(μ‐H)(μ‐H2B=NHR′)][BArF4] (LR=R2P(CH2)3PR2; R=Ph, iPr; R′=H, Me) form by addition of H3B⋅NMeR′H2 to [Rh(LR)(η6‐C6H5F)][BArF4]. DFT calculations demonstrate that the amino–borane interacts with the Rh centers through strong Rh‐H and Rh‐B interactions. Mechanistic investigations show that these dimers can form by a boronium‐mediated route, and are pre‐catalysts for amine‐borane dehydropolymerization, suggesting a possible role for bimetallic motifs in catalysis",

keywords = "Amino-borane, Dehydrocoupling, DFT, Catalytic mechanisms, Rhodium dimers",

author = "Amit Kumar and Nicholas Beatie and Pike, {Sebastian A} and Macgregor, {Stuart A.} and Weller, {Andrew S}",

note = "Funding: The EPSRC (A.S.W. and S.A.M., EP/M024210/1; N.A.B., DTP Studentship), the Rhodes Trust (A.K.), G. M. Adams (G. P. C. analysis).",

year = "2016",

month = may,

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doi = "10.1002/anie.201600898",

language = "English",

volume = "55",

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journal = "Angewandte Chemie International Edition",

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AU - Kumar, Amit

AU - Beatie, Nicholas

AU - Pike, Sebastian A

AU - Macgregor, Stuart A.

AU - Weller, Andrew S

N1 - Funding: The EPSRC (A.S.W. and S.A.M., EP/M024210/1; N.A.B., DTP Studentship), the Rhodes Trust (A.K.), G. M. Adams (G. P. C. analysis).

PY - 2016/5/27

Y1 - 2016/5/27

N2 - The μ‐amino–borane complexes [Rh2(LR)2(μ‐H)(μ‐H2B=NHR′)][BArF4] (LR=R2P(CH2)3PR2; R=Ph, iPr; R′=H, Me) form by addition of H3B⋅NMeR′H2 to [Rh(LR)(η6‐C6H5F)][BArF4]. DFT calculations demonstrate that the amino–borane interacts with the Rh centers through strong Rh‐H and Rh‐B interactions. Mechanistic investigations show that these dimers can form by a boronium‐mediated route, and are pre‐catalysts for amine‐borane dehydropolymerization, suggesting a possible role for bimetallic motifs in catalysis

AB - The μ‐amino–borane complexes [Rh2(LR)2(μ‐H)(μ‐H2B=NHR′)][BArF4] (LR=R2P(CH2)3PR2; R=Ph, iPr; R′=H, Me) form by addition of H3B⋅NMeR′H2 to [Rh(LR)(η6‐C6H5F)][BArF4]. DFT calculations demonstrate that the amino–borane interacts with the Rh centers through strong Rh‐H and Rh‐B interactions. Mechanistic investigations show that these dimers can form by a boronium‐mediated route, and are pre‐catalysts for amine‐borane dehydropolymerization, suggesting a possible role for bimetallic motifs in catalysis

KW - Amino-borane

KW - Dehydrocoupling

KW - DFT

KW - Catalytic mechanisms

KW - Rhodium dimers

U2 - 10.1002/anie.201600898

DO - 10.1002/anie.201600898

M3 - Article

SN - 1433-7851

VL - 55

SP - 6651

EP - 6656

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 23

ER -

The simplest amino‐borane H2B=NH2 trapped on a rhodium dimer: pre‐catalysts for amine–borane dehydropolymerization

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The simplest amino‐borane H₂B=NH₂ trapped on a rhodium dimer: pre‐catalysts for amine–borane dehydropolymerization