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Substituent effects in reduction-induced synthesis of ansa-titanocenes

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Abstract

Bis{(diphenylvinylsilyl)tetramethylcyclopentadienyl}titanium dichloride [TiCl2{η5-C5Me4(SiPh2CH=CH2)}2] (1) is reduced with a half molar equivalent of magnesium to the monochloride ([TiCl{η5-C5Me4(SiPh2CH=CH2)}2] (2), whereas one molar equivalent of magnesium affords the titanocene [Ti{η5-C5Me4(SiPh2CH=CH2)}{η5:η2-C5Me4(SiPh2CH=CH2)}] (3) stabilized by η2-coordination of one of the two vinyl groups to titanium(II). In the presence of excess magnesium, the vinyl moieties of 3 undergo intramolecular coupling to afford the ansa-titanocene [Ti(η5:η5:η2-C5Me4SiPh2CH=CHCH2CH2SiPh2C5Me4)] (4) possessing the η2-coordinated double bond in lateral position of its ansa-chain. The symmetrical ansa-titanocene [Ti(η5:η5:η2-C5Me4SiPh2CH2CH=CHCH2SiPh2C5Me4)] (5) was not obtained although its DFT-calculated energy is only slightly higher than that of 4. It is considered that transient 5 gives rise to non-identified tar-like by-products which inherently accompany the formation of 4.

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Acknowledgments

This research was supported by Czech Science Foundation (Project No. P207/12/2368). R. Gy. is grateful to Slovak Grant Agency VEGA (Project No. 1/0336/13).

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Authors and Affiliations

  1. J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, 182 23, Prague 8, Czech Republic

    Jiří Pinkas, Jiří Kubišta, Karel Mach & Michal Horáček

  2. Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40, Prague 2, Czech Republic

    Ivana Císařová & Róbert Gyepes

  3. Department of Chemistry, Faculty of Education, J. Selye University, Bratislavská cesta 3322, 945 01, Komárno, Slovak Republic

    Róbert Gyepes

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  1. Jiří Pinkas
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  2. Ivana Císařová
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  3. Róbert Gyepes
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  4. Jiří Kubišta
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  5. Karel Mach
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  6. Michal Horáček
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Correspondence to Michal Horáček.

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Pinkas, J., Císařová, I., Gyepes, R. et al. Substituent effects in reduction-induced synthesis of ansa-titanocenes. Transition Met Chem 41, 143–152 (2016). https://doi.org/10.1007/s11243-015-0006-3

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  • DOI: https://doi.org/10.1007/s11243-015-0006-3

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