Hydrogen- and fluorine-bridged disilyl cations and their use in catalytic C-F activation.
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 beta = 130 degrees . Both cations catalyze the hydrodefluorination reaction of alkyl and benzyl fluorides to give alkanes.
Panisch
Robin
R
Institut für Reine und Angewandte Chemie der Carl von Ossietzky Universität Oldenburg, Carl von Ossietzky Str. 9-11 D-26129 Oldenburg, Federal Republic of Germany.
Bolte
Michael
M
Müller
Thomas
T