Competition between Birch reduction and fluorine abstraction in reactions of hydrated electrons (H(2)O)(n)(-) with the isomers of di- and trifluorobenzene.

Hockendorf, R. F., Balaj, O. P. and Beyer, M. K. (2011) Competition between Birch reduction and fluorine abstraction in reactions of hydrated electrons (H(2)O)(n)(-) with the isomers of di- and trifluorobenzene. Physical Chemistry Chemical Physics, 13 (19). pp. 8924-8930. DOI 10.1039/c1cp20505f.

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Abstract

The reactions of the isomers of di- and trifluorobenzene with hydrated electrons (H(2)O)(n)(-), n = 19-70, have been studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. While Birch reduction, i.e. H atom transfer to the aromatic ring, was observed for all studied isomers, a strong dependence on the substitution pattern was observed for fluorine abstraction. Nanocalorimetry combined with G3 calculations are used to analyze the thermochemistry of the reactions. Fluorine abstraction is at least 100 kJ mol(-1) more exothermic than Birch reduction, yet the latter is the dominant reaction pathway for all three difluorobenzene isomers. Fluorine abstraction and Birch reduction face activation barriers of comparable magnitude. The relative barrier height is sensitive to the substitution pattern. Birch reduction occurs selectively with 1,3- and 1,4-difluorobenzene in a nanoscale aqueous

Document Type: Article
Keywords: negatively charged water ion-molecule reactions anaerobic aromatic metabolism gas-phase cluster anions unimolecular dissociation ab-initio photoelectron-spectroscopy temperature-dependence theoretical approach
Research affiliation: Kiel University
Refereed: Yes
DOI etc.: 10.1039/c1cp20505f
ISSN: 1463-9076
Date Deposited: 01 Nov 2012 05:06
Last Modified: 23 Jan 2013 10:01
URI: http://oceanrep.geomar.de/id/eprint/17537

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