Hydrodefluorination of non-activated C-F bonds by diisobutyl-aluminiumhydride via the aluminium cation [i-Bu2Al] |
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| Authors: | Marcus Klahn Anke Spannenberg Ingo Krossing |
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| Institution: | a Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, D-18059 Rostock, Germany
b Lehrstuhl für Molekül- und Koordinationschemie, Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Albert Str. 21, D-79104 Freiburg i. Br., Germany |
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| Abstract: | A novel system for the hydrodefluorination (HDF) of non-activated C-F bonds at room-temperature is described. The reaction of i-Bu2AlH with Ph3C]B(C6F5)4] (1), Ph3C]Al(C6F5)4] (2) and Ph3C]Al{OC(CF3)3}4] (3) as precatalysts leads under formation of triphenylmethane to the aluminium cation i-Bu2Al]+ and the non-coordinating anions M(C6F5)4]− (M = B, Al) and Al{OC(CF3)3}4]−. The formed aluminium cation is very reactive towards C-F bonds and easily forms i-Bu2AlF releasing a carbocation that abstracts the hydride of excess i-Bu2AlH and yields the corresponding hydrocarbon. Thereby, the active species i-Bu2Al]+ is regenerated and can realize a catalytic cycle. For 1-fluorohexane as an example including non-activated C-F bonds different activities were found (TON: 1: 20; 2: 12; 3: 30) in cyclohexane as solvent. |
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| Keywords: | Bond activation Hydrodefluorination Organoaluminium compounds Homogeneous catalysis Boranates Aluminates |
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