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^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

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Abstract

The rhodium complex [Rh(Ph₂PCH₂CH₂CH₂PPh₂)(η⁶-FC₆H₅)][BAr^F ₄], 2, catalyzes BH/BD exchange between D₂ and the boranes H₃B⋅NMe₃, H₃B⋅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: R₃B⋅NMeR₂ 1-d_x (R=H, D; x=0, 2, 3 or 5). It also acts to catalyze the dehydropolymerization of 1-d_x 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

Keywords

borane
dehydropolymerization
deuterium
H/D exchange
rhodium

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

abstract = "The rhodium complex [Rh(Ph2PCH2CH2CH2PPh2)(η6-FC6H5)][BArF 4], 2, catalyzes BH/BD exchange between D2 and the boranes H3B⋅NMe3, H3B⋅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: R3B⋅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.}",

year = "2018",

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doi = "10.1002/chem.201800737",

language = "English",

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journal = "Chemistry - A European Journal",

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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(Ph2PCH2CH2CH2PPh2)(η6-FC6H5)][BArF 4], 2, catalyzes BH/BD exchange between D2 and the boranes H3B⋅NMe3, H3B⋅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: R3B⋅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(Ph2PCH2CH2CH2PPh2)(η6-FC6H5)][BArF 4], 2, catalyzes BH/BD exchange between D2 and the boranes H3B⋅NMe3, H3B⋅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: R3B⋅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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U2 - 10.1002/chem.201800737

DO - 10.1002/chem.201800737

M3 - Article (Academic Journal)

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AN - SCOPUS:85044191570

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

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