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Dehydrocoupling of SiMe2H substituents in permethylated zirconocene complexes
- 1.0358453 - ÚFCH JH 2012 RIV CZ eng J - Journal Article
Pinkas, Jiří - Gyepes, R. - Císařová, I. - Kubišta, Jiří - Mach, Karel - Horáček, Michal
Dehydrocoupling of SiMe2H substituents in permethylated zirconocene complexes.
Collection of Czechoslovak Chemical Communications. Roč. 76, č. 3 (2011), s. 177-191. ISSN 0010-0765
R&D Projects: GA AV ČR IAA400400708; GA MŠMT(CZ) LC06070
Institutional research plan: CEZ:AV0Z40400503
Keywords : metallocenes * zirconium * bridging ligands
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 1.283, year: 2011
Complex [Zr{η5-C5Me4(SiMe2H)}2Cl2] (1) was prepared by the reaction of lithium salt of 2,3,4,5-tetramethyl-1-(dimethylsilyl)cyclopenta-2,4-diene with [ZrCl4] in boiling THF. The reduction of 1 with excess magnesium in THF in the presence of excess bis(trimethylsilyl)acetylene (btmsa) afforded the bivalent metal ansa-disilylene complex with π-coordinated btmsa [Zr(η2-btmsa){η5-C5Me4(SiMe2)}2] (2). The dehydrocoupling of SiMe2H groups was accompanied by a hydrogen transfer to releasing btmsa to give a mixture of cis- and trans-1,2-bis(trimethylsilyl)ethene. Chlorination of 2 with PbCl2 afforded ansa-[Zr{η5-C5Me4(SiMe2)}2Cl2] (3) and liberated btmsa. The crystal structures of complexes, 1, 2 and 3 have been determined by X-ray crystallography.
Permanent Link: http://hdl.handle.net/11104/0196493
Number of the records: 1