Acyclic Boryl Complexes of Copper(I)

Rex S.C. Charman; Josie A. Hobson; Ross A. Jackson; Mary F. Mahon; Samuel E. Neale; David J. Liptrot

doi:10.1002/chem.202302704

Acyclic Boryl Complexes of Copper(I)

Rex S.C. Charman, Josie A. Hobson, Ross A. Jackson, Mary F. Mahon, Samuel E. Neale, David J. Liptrot

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

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Abstract

Reaction of (6-Dipp)CuOtBu (6-Dipp=C{NDippCH₂}₂CH₂, Dipp=2,6-iPr₂C₆H₃) with B₂(OMe)₄ provided access to (6-Dipp)CuB(OMe)₂ via σ-bond metathesis. (6-Dipp)CuB(OMe)₂ was characterised by NMR spectroscopy and X-ray crystallography and shown to be a monomeric acyclic boryl of copper. (6-Dipp)CuB(OMe)₂ reacted with ethylene and diphenylacetylene to provide insertion compounds into the Cu-B bond which were characterised by NMR spectroscopy in both cases and X-ray crystallography in the latter. It was also competent in the rapid catalytic deoxygenation of CO₂ in the presence of excess B₂(OMe)₄. Alongside π-insertion, (6-Dipp)CuB(OMe)₂ reacted with LiNMe₂ to provide a salt metathesis reaction at boron, giving (6-Dipp)CuB(OMe)NMe₂, a second monomeric acyclic boryl, which also cuproborated diphenylacetylene. Computational interrogation validated these acyclic boryl species to be electronically similar to (6-Dipp)CuBpin.

Original language	English
Article number	e202302704
Journal	Chemistry - A European Journal
Volume	30
Issue number	1
Early online date	13 Nov 2023
DOIs	https://doi.org/10.1002/chem.202302704
Publication status	Published - 2 Jan 2024

Bibliographical note

Funding Information:
DJL thanks the Royal Society for the support of a University Research Fellowship. This research made use of the Anatra High Performance Computing (HPC) Services at the University of Bath. (University of Bath, Research Computing Group, DOI: https://doi.org/10.15125/b6cd‐s854 ). We also thank Dr Claire McMullin for use of the AIMAll and NBO software for electronic structure calculations.

Funding

DJL thanks the Royal Society for the support of a University Research Fellowship. This research made use of the Anatra High Performance Computing (HPC) Services at the University of Bath. (University of Bath, Research Computing Group, DOI: https://doi.org/10.15125/b6cd‐s854 ). We also thank Dr Claire McMullin for use of the AIMAll and NBO software for electronic structure calculations.

Funders	Funder number
Royal Society
University of Bath

Keywords

acyclic
boryl
copper
N-heterocyclic carbene

ASJC Scopus subject areas

Catalysis
General Chemistry
Organic Chemistry

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Cite this

@article{62a3fe4ba6f34bd4ae50a5b75244b19f,

title = "Acyclic Boryl Complexes of Copper(I)",

abstract = "Reaction of (6-Dipp)CuOtBu (6-Dipp=C\{NDippCH2\}2CH2, Dipp=2,6-iPr2C6H3) with B2(OMe)4 provided access to (6-Dipp)CuB(OMe)2 via σ-bond metathesis. (6-Dipp)CuB(OMe)2 was characterised by NMR spectroscopy and X-ray crystallography and shown to be a monomeric acyclic boryl of copper. (6-Dipp)CuB(OMe)2 reacted with ethylene and diphenylacetylene to provide insertion compounds into the Cu-B bond which were characterised by NMR spectroscopy in both cases and X-ray crystallography in the latter. It was also competent in the rapid catalytic deoxygenation of CO2 in the presence of excess B2(OMe)4. Alongside π-insertion, (6-Dipp)CuB(OMe)2 reacted with LiNMe2 to provide a salt metathesis reaction at boron, giving (6-Dipp)CuB(OMe)NMe2, a second monomeric acyclic boryl, which also cuproborated diphenylacetylene. Computational interrogation validated these acyclic boryl species to be electronically similar to (6-Dipp)CuBpin.",

keywords = "acyclic, boryl, copper, N-heterocyclic carbene",

author = "Charman, \{Rex S.C.\} and Hobson, \{Josie A.\} and Jackson, \{Ross A.\} and Mahon, \{Mary F.\} and Neale, \{Samuel E.\} and Liptrot, \{David J.\}",

note = "Funding Information: DJL thanks the Royal Society for the support of a University Research Fellowship. This research made use of the Anatra High Performance Computing (HPC) Services at the University of Bath. (University of Bath, Research Computing Group, DOI: https://doi.org/10.15125/b6cd‐s854 ). We also thank Dr Claire McMullin for use of the AIMAll and NBO software for electronic structure calculations. ",

year = "2024",

month = jan,

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doi = "10.1002/chem.202302704",

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volume = "30",

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T1 - Acyclic Boryl Complexes of Copper(I)

AU - Charman, Rex S.C.

AU - Hobson, Josie A.

AU - Jackson, Ross A.

AU - Mahon, Mary F.

AU - Neale, Samuel E.

AU - Liptrot, David J.

N1 - Funding Information: DJL thanks the Royal Society for the support of a University Research Fellowship. This research made use of the Anatra High Performance Computing (HPC) Services at the University of Bath. (University of Bath, Research Computing Group, DOI: https://doi.org/10.15125/b6cd‐s854 ). We also thank Dr Claire McMullin for use of the AIMAll and NBO software for electronic structure calculations.

PY - 2024/1/2

Y1 - 2024/1/2

N2 - Reaction of (6-Dipp)CuOtBu (6-Dipp=C{NDippCH2}2CH2, Dipp=2,6-iPr2C6H3) with B2(OMe)4 provided access to (6-Dipp)CuB(OMe)2 via σ-bond metathesis. (6-Dipp)CuB(OMe)2 was characterised by NMR spectroscopy and X-ray crystallography and shown to be a monomeric acyclic boryl of copper. (6-Dipp)CuB(OMe)2 reacted with ethylene and diphenylacetylene to provide insertion compounds into the Cu-B bond which were characterised by NMR spectroscopy in both cases and X-ray crystallography in the latter. It was also competent in the rapid catalytic deoxygenation of CO2 in the presence of excess B2(OMe)4. Alongside π-insertion, (6-Dipp)CuB(OMe)2 reacted with LiNMe2 to provide a salt metathesis reaction at boron, giving (6-Dipp)CuB(OMe)NMe2, a second monomeric acyclic boryl, which also cuproborated diphenylacetylene. Computational interrogation validated these acyclic boryl species to be electronically similar to (6-Dipp)CuBpin.

AB - Reaction of (6-Dipp)CuOtBu (6-Dipp=C{NDippCH2}2CH2, Dipp=2,6-iPr2C6H3) with B2(OMe)4 provided access to (6-Dipp)CuB(OMe)2 via σ-bond metathesis. (6-Dipp)CuB(OMe)2 was characterised by NMR spectroscopy and X-ray crystallography and shown to be a monomeric acyclic boryl of copper. (6-Dipp)CuB(OMe)2 reacted with ethylene and diphenylacetylene to provide insertion compounds into the Cu-B bond which were characterised by NMR spectroscopy in both cases and X-ray crystallography in the latter. It was also competent in the rapid catalytic deoxygenation of CO2 in the presence of excess B2(OMe)4. Alongside π-insertion, (6-Dipp)CuB(OMe)2 reacted with LiNMe2 to provide a salt metathesis reaction at boron, giving (6-Dipp)CuB(OMe)NMe2, a second monomeric acyclic boryl, which also cuproborated diphenylacetylene. Computational interrogation validated these acyclic boryl species to be electronically similar to (6-Dipp)CuBpin.

KW - acyclic

KW - boryl

KW - copper

KW - N-heterocyclic carbene

UR - https://www.scopus.com/pages/publications/85176297081

U2 - 10.1002/chem.202302704

DO - 10.1002/chem.202302704

M3 - Article

AN - SCOPUS:85176297081

SN - 0947-6539

VL - 30

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 1

M1 - e202302704

ER -

Acyclic Boryl Complexes of Copper(I)

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

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