Activation of biscyclopentadienyl hydride complexes of titanium and aluminum by NH- and OH-acids in the reactions of hydrogenation of olefins. Crystal and molecular structures of {(η5−Cp)2Ti(μ−H)2AlH]μ−N(C2H4)4O]}2 and [(η5−Cp)2Ti(μ−H(2AlH]2(μ−OC2H4OMe)[(μ1:μ5−C5H4)Ti(μ5−Cp)(μ−H)]2* |
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| Authors: | A I Sizov T M Zvukova V K Bel'sky B M Bulychev |
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| Institution: | 1. Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie Gory, 119899, Moscow, Russian Federation
2. State Research Center of the Russian Federation “L. Ya. Karpov Scientific-Research Physicochemical Institute”, 10 ul. Vorontsovo Pole, 117120, Moscow, Russian Federation
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| Abstract: | The reactions of Cp2TiH2AlH2·Et2O (1) with HN(C2H4)2O, HOC2H4OMe, and water afforded the complexes {Cp2TiH2AlHμ-N(C2H4)2O]}2 (5), Cp2TiH2AlH(μ-OC2H4OMe)]2 (6) and (Cp2TiH2AlH)2O (4), respectively. Compounds 5 and 6 are dimers containing bridging Al?E2?Al fragments (E=N or O). Complex 6 in solution converted to the hexanuclear compound (η5?Cp)2Ti(μ?H(2AlH]2(μ?OC2H4OMe)(μ1:μ5?C5H4)Ti(μ5?Cp)(μ?H)]2 (8). The structures of complexes 5 and 8 were established by X-ray diffraction analysis. The rates of hydrogenation of hex-1-ene were determined using compounds 4–6 and the complexes Cp2TiH2AlH(NEt2)]2 and Cp2TiH2AlH(OEt)]2 as catalysts. The probable mechanism of hydrogenation with the participation of bimetallic hydride complexes of aluminum and titanocene is discussed. |
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