Substituent effects in reduction-induced synthesis of ansa-titanocenes


Bis{(diphenylvinylsilyl)tetramethylcyclopentadienyl}titanium dichloride [TiCl25-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)}{η52-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(η552-C5Me4SiPh2CH=CHCH2CH2SiPh2C5Me4)] (4) possessing the η2-coordinated double bond in lateral position of its ansa-chain. The symmetrical ansa-titanocene [Ti(η552-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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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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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).

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  • Molar Equivalent
  • Titanocene
  • Titanocene Dichloride
  • SiH2Ph2
  • Titanium Dichloride