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

32 Citations (Scopus)

407 Downloads (Pure)

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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@article{716cfe8d3c7242ab836b4a53681d5b98,

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",

month = apr,

day = "11",

doi = "10.1002/chem.201800737",

language = "English",

volume = "24",

pages = "5450--5455",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley and Sons Inc",

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TY - JOUR

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

UR - https://www.scopus.com/pages/publications/85044191570

U2 - 10.1002/chem.201800737

DO - 10.1002/chem.201800737

M3 - Article (Academic Journal)

C2 - 29504649

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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