Substituent effects in reduction-induced synthesis of ansa-titanocenes

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• 作者：Jiří Pinkas ; Ivana Císařová ; Róbert Gyepes ; Jiří Kubišta…
• 刊名：Transition Metal Chemistry
• 出版年：2016
• 出版时间：March 2016
• 年：2016
• 卷：41
• 期：2
• 页码：143-152
• 全文大小：621 KB
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• 作者单位：Jiří Pinkas (1)
  Ivana Císařová (2)
  Róbert Gyepes (2) (3)
  Jiří Kubišta (1)
  Karel Mach (1)
  Michal Horáček (1)
  
  1. J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, 182 23, Prague 8, Czech Republic
  2. Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40, Prague 2, Czech Republic
  3. Department of Chemistry, Faculty of Education, J. Selye University, Bratislavská cesta 3322, 945 01, Komárno, Slovak Republic
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Catalysis
  Physical Chemistry
  Inorganic Chemistry
  
• 出版者：Springer Netherlands
• ISSN：1572-901X

文摘

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. Electronic supplementary materialThe online version of this article (doi:10.​1007/​s11243-015-0006-3) contains supplementary material, which is available to authorized users.