A stable ring-expanded NHC-supported copper boryl and its reactivity towards heterocumulenes

Thomas M. Horsley Downie; Rex S.C. Charman; Jonathan W. Hall; Mary F. Mahon; John P. Lowe; David J. Liptrot

doi:10.1039/d1dt03540a

A stable ring-expanded NHC-supported copper boryl and its reactivity towards heterocumulenes

Thomas M. Horsley Downie, Rex S.C. Charman, Jonathan W. Hall, Mary F. Mahon, John P. Lowe, David J. Liptrot

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

13 Citations (SciVal)

Abstract

Reaction of bis(pinacolato)diboron with (6-Dipp)CuOtBu generates a ring-expanded N-heterocyclic carbene supported copper(i) boryl, (6-Dipp)CuBpin. This compound showed remarkable stability and was characterised by NMR spectroscopy and X-ray crystallography. (6-Dipp)CuBpin readily dechalcogenated a range of heterocumulenes such as CO2, isocyanates and isothiocyanates to yield (6-Dipp)CuXBpin (X = O, S). In the case of CO2 catalytic reduction to CO is viable in the presence of excess bis(pinacolato)diboron. In contrast, in the case of iso(thio)cyanates, the isocyanide byproduct of dechalcogenation reacted with (6-Dipp)CuBpin to generate a copper(i) borylimidinate, (6-Dipp)CuC(NR)Bpin, which went on to react with heterocumulenes. This off-cycle reactivity gives selective access to a range of novel boron-containing heterocycles bonded to copper, but precludes catalytic reactivity.

Original language	English
Pages (from-to)	16336-16342
Number of pages	7
Journal	Dalton Transactions
Volume	50
Issue number	44
DOIs	https://doi.org/10.1039/d1dt03540a
Publication status	Published - 28 Nov 2021

Bibliographical note

Funding Information:
DJL thanks the Royal Society for the support of a University Research Fellowship. We acknowledge financial support from the EPSRC Centre for Doctoral Training in Catalysis (EP/L016443/1) for JWH.

Funding

DJL thanks the Royal Society for the support of a University Research Fellowship. We acknowledge financial support from the EPSRC Centre for Doctoral Training in Catalysis (EP/L016443/1) for JWH.

ASJC Scopus subject areas

Inorganic Chemistry

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title = "A stable ring-expanded NHC-supported copper boryl and its reactivity towards heterocumulenes",

abstract = "Reaction of bis(pinacolato)diboron with (6-Dipp)CuOtBu generates a ring-expanded N-heterocyclic carbene supported copper(i) boryl, (6-Dipp)CuBpin. This compound showed remarkable stability and was characterised by NMR spectroscopy and X-ray crystallography. (6-Dipp)CuBpin readily dechalcogenated a range of heterocumulenes such as CO2, isocyanates and isothiocyanates to yield (6-Dipp)CuXBpin (X = O, S). In the case of CO2 catalytic reduction to CO is viable in the presence of excess bis(pinacolato)diboron. In contrast, in the case of iso(thio)cyanates, the isocyanide byproduct of dechalcogenation reacted with (6-Dipp)CuBpin to generate a copper(i) borylimidinate, (6-Dipp)CuC(NR)Bpin, which went on to react with heterocumulenes. This off-cycle reactivity gives selective access to a range of novel boron-containing heterocycles bonded to copper, but precludes catalytic reactivity. ",

author = "{Horsley Downie}, {Thomas M.} and Charman, {Rex S.C.} and Hall, {Jonathan W.} and Mahon, {Mary F.} and Lowe, {John P.} and Liptrot, {David J.}",

note = "Funding Information: DJL thanks the Royal Society for the support of a University Research Fellowship. We acknowledge financial support from the EPSRC Centre for Doctoral Training in Catalysis (EP/L016443/1) for JWH. ",

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T1 - A stable ring-expanded NHC-supported copper boryl and its reactivity towards heterocumulenes

AU - Horsley Downie, Thomas M.

AU - Charman, Rex S.C.

AU - Hall, Jonathan W.

AU - Mahon, Mary F.

AU - Lowe, John P.

AU - Liptrot, David J.

N1 - Funding Information: DJL thanks the Royal Society for the support of a University Research Fellowship. We acknowledge financial support from the EPSRC Centre for Doctoral Training in Catalysis (EP/L016443/1) for JWH.

PY - 2021/11/28

Y1 - 2021/11/28

N2 - Reaction of bis(pinacolato)diboron with (6-Dipp)CuOtBu generates a ring-expanded N-heterocyclic carbene supported copper(i) boryl, (6-Dipp)CuBpin. This compound showed remarkable stability and was characterised by NMR spectroscopy and X-ray crystallography. (6-Dipp)CuBpin readily dechalcogenated a range of heterocumulenes such as CO2, isocyanates and isothiocyanates to yield (6-Dipp)CuXBpin (X = O, S). In the case of CO2 catalytic reduction to CO is viable in the presence of excess bis(pinacolato)diboron. In contrast, in the case of iso(thio)cyanates, the isocyanide byproduct of dechalcogenation reacted with (6-Dipp)CuBpin to generate a copper(i) borylimidinate, (6-Dipp)CuC(NR)Bpin, which went on to react with heterocumulenes. This off-cycle reactivity gives selective access to a range of novel boron-containing heterocycles bonded to copper, but precludes catalytic reactivity.

AB - Reaction of bis(pinacolato)diboron with (6-Dipp)CuOtBu generates a ring-expanded N-heterocyclic carbene supported copper(i) boryl, (6-Dipp)CuBpin. This compound showed remarkable stability and was characterised by NMR spectroscopy and X-ray crystallography. (6-Dipp)CuBpin readily dechalcogenated a range of heterocumulenes such as CO2, isocyanates and isothiocyanates to yield (6-Dipp)CuXBpin (X = O, S). In the case of CO2 catalytic reduction to CO is viable in the presence of excess bis(pinacolato)diboron. In contrast, in the case of iso(thio)cyanates, the isocyanide byproduct of dechalcogenation reacted with (6-Dipp)CuBpin to generate a copper(i) borylimidinate, (6-Dipp)CuC(NR)Bpin, which went on to react with heterocumulenes. This off-cycle reactivity gives selective access to a range of novel boron-containing heterocycles bonded to copper, but precludes catalytic reactivity.

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A stable ring-expanded NHC-supported copper boryl and its reactivity towards heterocumulenes

Abstract

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