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Hydrogen- and Fluorine-Bridged Disilyl Cations and Their Use in Catalytic C−F Activation

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posted on 2006-08-02, 00:00 authored by Robin Panisch, Michael Bolte, Thomas Müller
The hydrogen-bridged disilyl cation 6 with an 1,8-naphthalenediyl backbone was synthesized and was characterized by NMR spectroscopy and X-ray crystallography, supported by quantum mechanical computations. The SiHSi linkage is symmetrical, corresponding to a single minimum potential, and the structural parameters are in agreement with the presence of a two electron−three center bond in 6. Treatment of disilyl cation 6 with alkyl fluorides yields the disilylfluoronium ion 10. The SiFSi group in the disilyl fluoronium ion 10 is symmetrical with an average SiF bond length of 175.9(8) and a bent angle β = 130°. Both cations catalyze the hydrodefluorination reaction of alkyl and benzyl fluorides to give alkanes.