Acyclic Boryl Complexes of Copper(I).

Autor: Charman RSC; Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK., Hobson JA; Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK., Jackson RA; Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK., Mahon MF; Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK., Neale SE; Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK., Liptrot DJ; Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Jan 02; Vol. 30 (1), pp. e202302704. Date of Electronic Publication: 2023 Nov 13.
DOI: 10.1002/chem.202302704
Abstrakt: Reaction of (6-Dipp)CuOtBu (6-Dipp=C{NDippCH 2 } 2 CH 2 , Dipp=2,6-iPr 2 C 6 H 3 ) with B 2 (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 CO 2 in the presence of excess B 2 (OMe) 4 . Alongside π-insertion, (6-Dipp)CuB(OMe) 2 reacted with LiNMe 2 to provide a salt metathesis reaction at boron, giving (6-Dipp)CuB(OMe)NMe 2 , a second monomeric acyclic boryl, which also cuproborated diphenylacetylene. Computational interrogation validated these acyclic boryl species to be electronically similar to (6-Dipp)CuBpin.
(© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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