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• W2016204797 startingPage "2635" @default.
• W2016204797 abstract "The complex [TiCl2{η5-C5Me4(SiMe2H)}2] (3) was prepared by reacting the lithium salt of 2,3,4,5-tetramethyl-1-(dimethylsilyl)cyclopenta-2,4-diene (1) with [TiCl3(THF)3] followed by chlorination of the formed [TiCl{η5-C5Me4(SiMe2H)}2] (2) with PbCl2. The reduction of 3 with excess magnesium in THF in the presence of excess bis(trimethylsilyl)ethyne (btmse) afforded the bivalent metal ansa disilylene complex with π-coordinated btmse [Ti{η5-C5Me4(SiMe2)}2(η2-btmse)] (4). The dehydrocoupling of the SiMe2H groups was accompanied by hydrogen transfer to the free btmse. Analogous reduction of 3 with magnesium in the presence of ethene gave a mixture of titanocene [Ti{η5-C5Me4(SiMe2Et)}2] (5) and its ethene complex [Ti{η5-C5Me4(SiMe2Et)}2(η2-C2H4)] (6). The latter complex is however unstable in this mixture and rearranges with evolution of ethane to [Ti{η5-C5Me4(SiMe2Et)}{η5:η2-C5Me4(SiMe2CH═CH2)}] (7), which has its vinyl group attached by π-coordination to Ti(II). The chlorination of 4 by PbCl2 yields ansa-[TiCl2{η5-C5Me4(SiMe2)}2] (8), liberating the btmse ligand. Complex 8 is reduced with a half-equivalent of Mg to give ansa-[TiCl{η5-C5Me4(SiMe2)}2] (9). Compounds 5, 6, and 7 were identified by 1H, 13C, and 29Si NMR spectra. The crystal structures of complexes 3, 4, and 9 have been determined by X-ray crystallography." @default.
• W2016204797 created "2016-06-24" @default.
• W2016204797 creator A5004234786 @default.
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• W2016204797 creator A5061738046 @default.
• W2016204797 date "2008-05-08" @default.
• W2016204797 modified "2023-09-23" @default.
• W2016204797 title "Reactivity of SiMe₂H Substituents in Permethylated Titanocene Complexes: Dehydrocoupling and Ethene Hydrosilylation" @default.
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• W2016204797 doi "https://doi.org/10.1021/om8000789" @default.
• W2016204797 hasPublicationYear "2008" @default.
• W2016204797 type Work @default.

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