The Simplest Amino-borane H2B=NH2 Trapped on a Rhodium Dimer: Pre-Catalysts for Amine-Borane Dehydropolymerization

Amit Kumar; Nicholas Beattie; Sebastian D Pike; Stuart Alan 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 Beattie, Sebastian D Pike, Stuart Alan Macgregor, Andrew S Weller

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Abstract

The μ-amino-borane complexes [Rh2(LR)2(μ-H)(μ-H2B=NHR′)][BArF 4] (LR=R2P(CH2)3PR2; R=Ph, iPr; R′=H, Me) form by addition of H3B NMeR′H2 to [Rh(LR)(η6-C6H5F)][BArF 4]. 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
Number of pages	6
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 - 1 Jun 2016

Keywords

Amino-borane
Catalytic mechanisms
Dehydrocoupling
DFT
Rhodium dimers

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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′)][BArF 4] (LR=R2P(CH2)3PR2; R=Ph, iPr; R′=H, Me) form by addition of H3B NMeR′H2 to [Rh(LR)(η6-C6H5F)][BArF 4]. 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, Catalytic mechanisms, Dehydrocoupling, DFT, Rhodium dimers",

author = "Amit Kumar and Nicholas Beattie and Pike, {Sebastian D} and Macgregor, {Stuart Alan} and Weller, {Andrew S}",

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T2 - Pre-Catalysts for Amine-Borane Dehydropolymerization

AU - Kumar, Amit

AU - Beattie, Nicholas

AU - Pike, Sebastian D

AU - Macgregor, Stuart Alan

AU - Weller, Andrew S

PY - 2016/6/1

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N2 - The μ-amino-borane complexes [Rh2(LR)2(μ-H)(μ-H2B=NHR′)][BArF 4] (LR=R2P(CH2)3PR2; R=Ph, iPr; R′=H, Me) form by addition of H3B NMeR′H2 to [Rh(LR)(η6-C6H5F)][BArF 4]. 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′)][BArF 4] (LR=R2P(CH2)3PR2; R=Ph, iPr; R′=H, Me) form by addition of H3B NMeR′H2 to [Rh(LR)(η6-C6H5F)][BArF 4]. 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 - Catalytic mechanisms

KW - Dehydrocoupling

KW - DFT

KW - Rhodium dimers

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The Simplest Amino-borane H2B=NH2 Trapped on a Rhodium Dimer: Pre-Catalysts for Amine-Borane Dehydropolymerization

Abstract

Keywords

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