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Issue 30, 2009
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Aromatic C–F activation by complexes containing the {Pt2S2} core via nucleophilic substitution: a combined experimental and theoretical study

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Abstract

The C–F bond activation of perfluorobenzene and perfluoropyridine have been achieved by means of the complex [Pt2(μ-S)2(dppp)2], where dppp denotes 1,3-bis(diphenylphosphino)propane. The reaction with the first substrate requires a long time (five days) and high temperature (reflux in toluene) to yield [Pt(o-S2C6F4)(dppp)] and [Pt33-S)2(dppp)3]F2, and involves replacement of two fluorides in the ortho position. In contrast, the reaction with perfluoropyridine is much faster (15 min at 0 °C) yielding [Pt2(μ-S){μ-(p-SC5F4N)}(dppp)2]F, which implies the C–F activation in the para position with respect the pyridine nitrogen. The mechanism of both reactions has been studied computationally and the geometries of the transition states are consistent with an SNAr mechanism where a sulfido bridging ligand replaces the fluoride anion. The energy barriers corresponding to the first and the second fluoride substitution are 131.7 and 137.1 kJ mol−1 for perfluorobenzene and 85.9 and 142.7 kJ mol−1 for perfluoropyridine, respectively. The different energy barrier of the first substitution explains the different experimental conditions required and the various products obtained for these reactions.

Graphical abstract: Aromatic C–F activation by complexes containing the {Pt2S2} core via nucleophilic substitution: a combined experimental and theoretical study

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Publication details

The article was received on 26 Jan 2009, accepted on 13 May 2009 and first published on 27 May 2009


Article type: Paper
DOI: 10.1039/B901697J
Citation: Dalton Trans., 2009,0, 5980-5988

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    Aromatic C–F activation by complexes containing the {Pt2S2} core via nucleophilic substitution: a combined experimental and theoretical study

    A. Nova, R. Mas-Ballesté, G. Ujaque, P. González-Duarte and A. Lledós, Dalton Trans., 2009, 0, 5980
    DOI: 10.1039/B901697J

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