Robust dicopper(i) μ-boryl complexes supported by a dinucleating naphthyridine-based ligand

Abstract

Copper boryl species have been widely invoked as reactive intermediates in Cu-catalysed C–H borylation reactions, but their isolation and study have been challenging. Use of the robust dinucleating ligand DPFN (2,7-bis(fluoro-di(2-pyridyl)methyl)-1,8-naphthyridine) allowed for the isolation of two very thermally stable dicopper(I) boryl complexes, [(DPFN)Cu2(μ-Bpin)][NTf2] (2) and [(DPFN)Cu2(μ-Bcat)][NTf2] (4) (pin = 2,3-dimethylbutane-2,3-diol; cat = benzene-1,2-diol). These complexes were prepared by cleavage of the corresponding diborane via reaction with the alkoxide [(DPFN)Cu2(μ-OtBu)][NTf2] (3). Reactivity studies illustrated the exceptional stability of these boryl complexes (thermal stability in solution up to 100 °C) and their role in the activation of C(sp)–H bonds. X-ray diffraction and computational studies provide a detailed description of the bonding and electronic structures in these complexes, and suggest that the dinucleating character of the naphthyridine-based ligand is largely responsible for their remarkable stability.

Graphical abstract: Robust dicopper(i) μ-boryl complexes supported by a dinucleating naphthyridine-based ligand

Supplementary files

Article information

Article type
Edge Article
Submitted
10 Feb 2022
Accepted
05 May 2022
First published
13 May 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022, Advance Article

Robust dicopper(I) μ-boryl complexes supported by a dinucleating naphthyridine-based ligand

P. Ríos, M. S. See, R. C. Handford, S. J. Teat and T. D. Tilley, Chem. Sci., 2022, Advance Article , DOI: 10.1039/D2SC00848C

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