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Issue 19, 2019
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Synthesis and reduction chemistry of mixed-Lewis-base-stabilised chloroborylenes

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Abstract

The one-electron reduction of (CAACMe)BCl3 (CAACMe = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) yields the dichloroboryl radical [(CAACMe)BCl2]˙. Furthermore, the twofold reduction of (CAACMe)BCl3 in the presence of a range of Lewis bases (L = CAACMe, N-heterocyclic carbene, phosphine) yields a series of doubly base-supported (CAACMe)LBCl chloroborylenes, all of which were structurally characterised. NMR and UV-vis spectroscopic and electrochemical data for (CAACMe)LBCl show that the boron centre becomes more electron-rich and the HOMO–LUMO gap widens as L becomes less π-accepting. A [(CAACMe)BCl2] boryl anion coordination polymer was isolated as a potential intermediate in these reductions. In most cases the reduction of the chloroborylenes resulted in the formation of the corresponding hydroborylenes or derivatives thereof, as well as ligand C–H activation products.

Graphical abstract: Synthesis and reduction chemistry of mixed-Lewis-base-stabilised chloroborylenes

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Article information


Submitted
01 Mar 2019
Accepted
06 Apr 2019
First published
08 Apr 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2019,10, 5095-5103
Article type
Edge Article

Synthesis and reduction chemistry of mixed-Lewis-base-stabilised chloroborylenes

M. Arrowsmith, J. I. Schweizer, M. Heinz, M. Härterich, I. Krummenacher, M. C. Holthausen and H. Braunschweig, Chem. Sci., 2019, 10, 5095
DOI: 10.1039/C9SC01039D

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