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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*

  • Organometallic Chemistry
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Russian Chemical Bulletin Aims and scope

Abstract

The reactions of Cp2TiH2AlH2·Et2O (1) with HN(C2H4)2O, HOC2H4OMe, and water afforded the complexes {Cp2TiH2AlH[μ-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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Authors and Affiliations

  1. Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie Gory, 119899, Moscow, Russian Federation

    A. I. Sizov, T. M. Zvukova & B. M. Bulychev

  2. State Research Center of the Russian Federation “L. Ya. Karpov Scientific-Research Physicochemical Institute”, 10 ul. Vorontsovo Pole, 117120, Moscow, Russian Federation

    V. K. Bel'sky

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  1. A. I. Sizov
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  2. T. M. Zvukova
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  3. V. K. Bel'sky
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  4. B. M. Bulychev
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Dedicated to the memory of Academician M. E. Vol'pin timed to his 75th birthday.

Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1216–1222, June, 1998.

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Sizov, A.I., Zvukova, T.M., Bel'sky, V.K. et al. 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*. Russ Chem Bull 47, 1186–1192 (1998). https://doi.org/10.1007/BF02503495

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  • DOI: https://doi.org/10.1007/BF02503495

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