A General, Rhodium-Catalyzed, Synthesis of Deuterated Boranes and N-Methyl Polyaminoboranes

Annie L Colebatch; Benjamin W Hawkey Gilder; George R Whittell; Nicola L Oldroyd; Ian Manners; Andrew S Weller

doi:10.1002/chem.201800737

A General, Rhodium-Catalyzed, Synthesis of Deuterated Boranes and N-Methyl Polyaminoboranes

Annie L Colebatch, Benjamin W Hawkey Gilder, George R Whittell, Nicola L Oldroyd, Ian Manners, Andrew S Weller

Chemistry

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

Abstract

The rhodium complex [Rh(Ph2 PCH2 CH2 CH2 PPh2 )(η6 -FC6 H5 )][BArF4 ], 2, catalyzes BH/BD exchange between D2 and the boranes H3 B⋅NMe3 , H3 B⋅SMe2 and HBpin, facilitating the expedient isolation of a variety of deuterated analogues in high isotopic purities, and in particular the isotopologues of N-methylamine-borane: R3 B⋅NMeR2 1-dx (R=H, D; x=0, 2, 3 or 5). It also acts to catalyze the dehydropolymerization of 1-dx to give deuterated polyaminoboranes. Mechanistic studies suggest a metal-based polymerization involving an unusual hybrid coordination insertion chain-growth/step-growth mechanism.

Original language	English
Pages (from-to)	5450-5455
Number of pages	6
Journal	Chemistry - A European Journal
Volume	24
Issue number	21
Early online date	23 Mar 2018
DOIs	https://doi.org/10.1002/chem.201800737
Publication status	Published - 11 Apr 2018

Bibliographical note

Keywords

borane
dehydropolymerization
deuterium
H/D exchange
rhodium

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10.1002/chem.201800737

https://ora.ox.ac.uk/objects/uuid:94232654-973f-402f-b3a1-431a8e1756bb

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title = "A General, Rhodium-Catalyzed, Synthesis of Deuterated Boranes and N-Methyl Polyaminoboranes",

abstract = "The rhodium complex [Rh(Ph2 PCH2 CH2 CH2 PPh2 )(η6 -FC6 H5 )][BArF4 ], 2, catalyzes BH/BD exchange between D2 and the boranes H3 B⋅NMe3 , H3 B⋅SMe2 and HBpin, facilitating the expedient isolation of a variety of deuterated analogues in high isotopic purities, and in particular the isotopologues of N-methylamine-borane: R3 B⋅NMeR2 1-dx (R=H, D; x=0, 2, 3 or 5). It also acts to catalyze the dehydropolymerization of 1-dx to give deuterated polyaminoboranes. Mechanistic studies suggest a metal-based polymerization involving an unusual hybrid coordination insertion chain-growth/step-growth mechanism.",

keywords = "borane, dehydropolymerization, deuterium, H/D exchange, rhodium",

author = "Colebatch, {Annie L} and {Hawkey Gilder}, {Benjamin W} and Whittell, {George R} and Oldroyd, {Nicola L} and Ian Manners and Weller, {Andrew S}",

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T1 - A General, Rhodium-Catalyzed, Synthesis of Deuterated Boranes and N-Methyl Polyaminoboranes

AU - Colebatch, Annie L

AU - Hawkey Gilder, Benjamin W

AU - Whittell, George R

AU - Oldroyd, Nicola L

AU - Manners, Ian

AU - Weller, Andrew S

PY - 2018/4/11

Y1 - 2018/4/11

N2 - The rhodium complex [Rh(Ph2 PCH2 CH2 CH2 PPh2 )(η6 -FC6 H5 )][BArF4 ], 2, catalyzes BH/BD exchange between D2 and the boranes H3 B⋅NMe3 , H3 B⋅SMe2 and HBpin, facilitating the expedient isolation of a variety of deuterated analogues in high isotopic purities, and in particular the isotopologues of N-methylamine-borane: R3 B⋅NMeR2 1-dx (R=H, D; x=0, 2, 3 or 5). It also acts to catalyze the dehydropolymerization of 1-dx to give deuterated polyaminoboranes. Mechanistic studies suggest a metal-based polymerization involving an unusual hybrid coordination insertion chain-growth/step-growth mechanism.

AB - The rhodium complex [Rh(Ph2 PCH2 CH2 CH2 PPh2 )(η6 -FC6 H5 )][BArF4 ], 2, catalyzes BH/BD exchange between D2 and the boranes H3 B⋅NMe3 , H3 B⋅SMe2 and HBpin, facilitating the expedient isolation of a variety of deuterated analogues in high isotopic purities, and in particular the isotopologues of N-methylamine-borane: R3 B⋅NMeR2 1-dx (R=H, D; x=0, 2, 3 or 5). It also acts to catalyze the dehydropolymerization of 1-dx to give deuterated polyaminoboranes. Mechanistic studies suggest a metal-based polymerization involving an unusual hybrid coordination insertion chain-growth/step-growth mechanism.

KW - borane

KW - dehydropolymerization

KW - deuterium

KW - H/D exchange

KW - rhodium

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SN - 0947-6539

VL - 24

SP - 5450

EP - 5455

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 21

ER -

A General, Rhodium-Catalyzed, Synthesis of Deuterated Boranes and N-Methyl Polyaminoboranes

Abstract

Bibliographical note

Keywords

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