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

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. (2021) A stable ring-expanded NHC-supported copper boryl and its reactivity towards heterocumulenes. Dalton Transactions, 50 (44). pp. 16336-16342. ISSN 1477-9234 (https://doi.org/10.1039/D1DT03540A)

[thumbnail of Horsley-Downie-etal-DT-2021-A-stable-ring-expanded-NHC-supported-copper-boryl]
Preview
Text. Filename: Horsley-Downie-etal-DT-2021-A-stable-ring-expanded-NHC-supported-copper-boryl.pdf
Final Published Version
License: Creative Commons Attribution-NonCommercial 3.0 logo

Download (2MB)| Preview

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.