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Issue 42, 2016
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Improving selectivity in catalytic hydrodefluorination by limiting SNV reactivity

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Abstract

Catalytic hydrodefluorination of perfluoroallylbenzene with Cp2TiH in THF is unselective and yields a variety of previously unknown compounds, predominantly activated in the allylic position. Several different mechanisms have been examined in detail using solvent corrected (THF) DFT(M06-2X) calculations for the archetypal perfluorinated olefin perfluoropropene and perfluoroallylbenzene: (a) single electron transfer, (b) hydrometallation/fluoride elimination, (c) σ-bond metathesis (allylic or vinylic), and (d) nucleophilic vinylic substitution (SNV, w/o Ti–F contacts in the TS). SNV is shown to be a competitive mechanism to hydrometallation and proceeds via ionic species from which F-elimination is facile and unselective leading to low selectivity in polar solvents. Subsequent experiments show that selectivity can be increased in a non-polar solvent.

Graphical abstract: Improving selectivity in catalytic hydrodefluorination by limiting SNV reactivity

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Supplementary files

Article information


Submitted
26 Jul 2016
Accepted
17 Aug 2016
First published
18 Aug 2016

This article is Open Access

Dalton Trans., 2016,45, 16789-16798
Article type
Paper

Improving selectivity in catalytic hydrodefluorination by limiting SNV reactivity

J. Krüger, C. Ehm and D. Lentz, Dalton Trans., 2016, 45, 16789 DOI: 10.1039/C6DT02961B

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