Intramolecular activation of pendant alkenyl group as a tool for modification of the zirconocene framework

0361646 - ÚFCH JH 2012 RIV NL eng J - Článek v odborném periodiku
Lamač, Martin - Horáček, Michal - Kubišta, Jiří - Pinkas, Jiří
Intramolecular activation of pendant alkenyl group as a tool for modification of the zirconocene framework.
Inorganica chimica acta. Roč. 373, č. 1 (2011), s. 291-294. ISSN 0020-1693. E-ISSN 1873-3255
Grant CEP: GA ČR GA203/09/1574; GA ČR GPP207/10/P200; GA MŠMT(CZ) LC06070
Výzkumný záměr: CEZ:AV0Z40400503
Klíčová slova: ,etallocenes * zirconium * benzyne complexes
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 1.846, rok: 2011

The diphenyl zirconocene [(eta(5)-C(5)H(5)){eta(5)-C(5)H(4)CMe(2)(CH(2))(2)CH=CH(2)}ZrPh(2)] (2) was readily obtained from the corresponding zirconocene dichloride 1 and two equivalents of phenyllithium. Upon thermal treatment at 80 degrees C, complex 2 released benzene, with concomitant activation of the pendant double bond and formation of intramolecularly alpha-tethered zirconaindane [(eta(5)-C(5)H(5)){eta(5), eta(1), eta(1)-C(5)H(4)CMe(2)(CH(2))(2)CHCH(2)C(6)H(4)}Zr] (3). Both Zr-C sigma-bonds in 3 easily undergo nucleophilic reactions with two equivalents of HCl or one equivalent of Cl(2)PPh giving rise to zirconocene dichlorides with pendant phenyl group [(eta(5)-C(5)H(5)){eta(5)-C(5)H(4)CMe(2)(CH(2))(4)Ph}ZrCl(2)] (4) or with 1-phenylphosphindolinyl moiety [(eta(5)-C(5)H(5)){eta(5)-C(5)H(4)CMe(2)(CH(2))(2)cyclo-CHCH(2)C(6)H(4)P(Ph)}ZrCl(2)] (5), respectively.
Trvalý link: http://hdl.handle.net/11104/0198913