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Issue 3, 2002
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A computational study of the mechanism of palladium insertion into alkynyl and aryl carbon–fluorine bonds

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Abstract

An ab initio molecular orbital study using both gas-phase and B3LYP/DZVP-COSMO solvation models of the mechanism of palladium insertion into alkyne and aryl carbon–halogen bonds suggests that the mechanism of palladium insertion into alkyne species can proceed via a concerted oxidative addition across the carbon–halogen bond. A stepwise mechanism via a σ-complex is favoured when a nitro group is introduced onto the alkyne. The palladium insertion into variously substituted aryl fluorides was again found to proceed via a single-step concerted mechanism, and although a σ-complex can be located when 2,4-dinitro and 2-nitro substitution is present, the energy of this stepwise route is very similar to the concerted pathway and no clear decision on the pathway can be made. No intermediate σ-complex could be located for η6-tricarbonylchromium-complexed fluorobenzene, and only a concerted pathway was identified.

Graphical abstract: A computational study of the mechanism of palladium insertion into alkynyl and aryl carbon–fluorine bonds

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Supplementary files

Article information


Submitted
25 Sep 2001
Accepted
17 Dec 2001
First published
25 Jan 2002

J. Chem. Soc., Perkin Trans. 2, 2002, 576-581
Article type
Paper

A computational study of the mechanism of palladium insertion into alkynyl and aryl carbon–fluorine bonds

M. Jakt, L. Johannissen, H. S. Rzepa, D. A. Widdowson and R. Wilhelm, J. Chem. Soc., Perkin Trans. 2, 2002, 576
DOI: 10.1039/B108727B

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