Ring-Expanded N-Heterocyclic Copper(I) Boryl Complexes: The Structures of [(6-Dipp)CuBcat], [(6-Dipp)CuBneop], and [(6-Dipp)CuBhex]

Dawid J. Babula; Rex S.C. Charman; Thomas H. Jerome; Thomas M. Horsley Downie; Mary F. Mahon; David J. Liptrot

doi:10.1002/ejic.202300043

Ring-Expanded N-Heterocyclic Copper(I) Boryl Complexes: The Structures of [(6-Dipp)CuBcat], [(6-Dipp)CuBneop], and [(6-Dipp)CuBhex]

Dawid J. Babula, Rex S.C. Charman, Thomas H. Jerome, Thomas M. Horsley Downie, Mary F. Mahon, David J. Liptrot

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

Abstract

σ-Bond metathesis reactions between [(6-Dipp)CuOtBu] (6-Dipp=:C({Dipp}NCH₂)₂CH₂, Dipp=2,6-iPr₂−C₆H₃) and three diboranes gave access to three new copper(I) boryl complexes [(6-Dipp)CuBcat], [(6-Dipp)CuBneop], and [(6-Dipp)CuBhex] (cat=1,2-O₂C₆H₄; neop=(OCH₂)₂C(CH₃)₂; hex=OC(CH₃)HCH₂C(CH₃)₂O). Whilst [(6-Dipp)CuBcat] and [(6-Dipp)CuBneop] formed rapidly in toluene, access to [(6-Dipp)CuBhex] required heating to 60 °C for days. The complexes were characterised by single-crystal X-ray crystallography which showed in all three cases that the systems were monomers and distorted-linear at the copper atom. The stability of [(6-Dipp)CuBneop] was found to be comparable to that of [(IPr*)Cu-Bneop] (IPr*=1,3-bis(2,6-(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene); it persisted in solution for days with no sign of decomposition. [(6-Dipp)CuBhex] is a rare crystallographically characterised example of a complex containing a boryl anion supported by the hexylene glycolato ligand.

Original language	English
Article number	e202300043
Journal	European Journal of Inorganic Chemistry
Early online date	27 Feb 2023
DOIs	https://doi.org/10.1002/ejic.202300043
Publication status	E-pub ahead of print - 27 Feb 2023

Keywords

boron
boryl anion
carbene ligands
copper
ring-expanded N-heterocyclic carbene

ASJC Scopus subject areas

Inorganic Chemistry

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10.1002/ejic.202300043Licence: CC BY

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@article{987990666b7e45808af391323d92b5e9,

title = "Ring-Expanded N-Heterocyclic Copper(I) Boryl Complexes: The Structures of [(6-Dipp)CuBcat], [(6-Dipp)CuBneop], and [(6-Dipp)CuBhex]",

abstract = "σ-Bond metathesis reactions between [(6-Dipp)CuOtBu] (6-Dipp=:C({Dipp}NCH2)2CH2, Dipp=2,6-iPr2−C6H3) and three diboranes gave access to three new copper(I) boryl complexes [(6-Dipp)CuBcat], [(6-Dipp)CuBneop], and [(6-Dipp)CuBhex] (cat=1,2-O2C6H4; neop=(OCH2)2C(CH3)2; hex=OC(CH3)HCH2C(CH3)2O). Whilst [(6-Dipp)CuBcat] and [(6-Dipp)CuBneop] formed rapidly in toluene, access to [(6-Dipp)CuBhex] required heating to 60 °C for days. The complexes were characterised by single-crystal X-ray crystallography which showed in all three cases that the systems were monomers and distorted-linear at the copper atom. The stability of [(6-Dipp)CuBneop] was found to be comparable to that of [(IPr*)Cu-Bneop] (IPr*=1,3-bis(2,6-(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene); it persisted in solution for days with no sign of decomposition. [(6-Dipp)CuBhex] is a rare crystallographically characterised example of a complex containing a boryl anion supported by the hexylene glycolato ligand.",

keywords = "boron, boryl anion, carbene ligands, copper, ring-expanded N-heterocyclic carbene",

author = "Babula, {Dawid J.} and Charman, {Rex S.C.} and Jerome, {Thomas H.} and {Horsley Downie}, {Thomas M.} and Mahon, {Mary F.} and Liptrot, {David J.}",

note = "Funding Information: DJL thanks the Royal Society for the support of a University Research Fellowship. We wish to thank the University of Bath for funding and MC for use of their analytical facilities. 2 Royal Society - URF\R1\191066 Data Availability Statement The data that support the findings of this study are available in the supplementary material of this article.",

year = "2023",

month = feb,

day = "27",

doi = "10.1002/ejic.202300043",

language = "English",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

}

TY - JOUR

T1 - Ring-Expanded N-Heterocyclic Copper(I) Boryl Complexes

T2 - The Structures of [(6-Dipp)CuBcat], [(6-Dipp)CuBneop], and [(6-Dipp)CuBhex]

AU - Babula, Dawid J.

AU - Charman, Rex S.C.

AU - Jerome, Thomas H.

AU - Horsley Downie, Thomas M.

AU - Mahon, Mary F.

AU - Liptrot, David J.

N1 - Funding Information: DJL thanks the Royal Society for the support of a University Research Fellowship. We wish to thank the University of Bath for funding and MC for use of their analytical facilities. 2 Royal Society - URF\R1\191066 Data Availability Statement The data that support the findings of this study are available in the supplementary material of this article.

PY - 2023/2/27

Y1 - 2023/2/27

N2 - σ-Bond metathesis reactions between [(6-Dipp)CuOtBu] (6-Dipp=:C({Dipp}NCH2)2CH2, Dipp=2,6-iPr2−C6H3) and three diboranes gave access to three new copper(I) boryl complexes [(6-Dipp)CuBcat], [(6-Dipp)CuBneop], and [(6-Dipp)CuBhex] (cat=1,2-O2C6H4; neop=(OCH2)2C(CH3)2; hex=OC(CH3)HCH2C(CH3)2O). Whilst [(6-Dipp)CuBcat] and [(6-Dipp)CuBneop] formed rapidly in toluene, access to [(6-Dipp)CuBhex] required heating to 60 °C for days. The complexes were characterised by single-crystal X-ray crystallography which showed in all three cases that the systems were monomers and distorted-linear at the copper atom. The stability of [(6-Dipp)CuBneop] was found to be comparable to that of [(IPr*)Cu-Bneop] (IPr*=1,3-bis(2,6-(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene); it persisted in solution for days with no sign of decomposition. [(6-Dipp)CuBhex] is a rare crystallographically characterised example of a complex containing a boryl anion supported by the hexylene glycolato ligand.

AB - σ-Bond metathesis reactions between [(6-Dipp)CuOtBu] (6-Dipp=:C({Dipp}NCH2)2CH2, Dipp=2,6-iPr2−C6H3) and three diboranes gave access to three new copper(I) boryl complexes [(6-Dipp)CuBcat], [(6-Dipp)CuBneop], and [(6-Dipp)CuBhex] (cat=1,2-O2C6H4; neop=(OCH2)2C(CH3)2; hex=OC(CH3)HCH2C(CH3)2O). Whilst [(6-Dipp)CuBcat] and [(6-Dipp)CuBneop] formed rapidly in toluene, access to [(6-Dipp)CuBhex] required heating to 60 °C for days. The complexes were characterised by single-crystal X-ray crystallography which showed in all three cases that the systems were monomers and distorted-linear at the copper atom. The stability of [(6-Dipp)CuBneop] was found to be comparable to that of [(IPr*)Cu-Bneop] (IPr*=1,3-bis(2,6-(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene); it persisted in solution for days with no sign of decomposition. [(6-Dipp)CuBhex] is a rare crystallographically characterised example of a complex containing a boryl anion supported by the hexylene glycolato ligand.

KW - boron

KW - boryl anion

KW - carbene ligands

KW - copper

KW - ring-expanded N-heterocyclic carbene

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U2 - 10.1002/ejic.202300043

DO - 10.1002/ejic.202300043

M3 - Article

AN - SCOPUS:85148903407

SN - 1434-1948

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

M1 - e202300043

ER -

Ring-Expanded N-Heterocyclic Copper(I) Boryl Complexes: The Structures of [(6-Dipp)CuBcat], [(6-Dipp)CuBneop], and [(6-Dipp)CuBhex]

Abstract

Keywords

ASJC Scopus subject areas

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