Počet záznamů: 1

TITANOCENE AND ansa-TITANOCENE COMPLEXES BEARING 2,6-BIS(ISOPROPYL)PHENOXIDE LIGAND(S). SYNTHESES, CHARACTERIZATION AND USE IN CATALYTIC DEHYDROCOUPLING POLYMERIZATION OF PHENYLSILANE

  1. 1.
    0358409 - UFCH-W 2012 RIV CZ eng J - Článek v odborném periodiku
    Horáček, Michal - Merna, J. - Gyepes, R. - Sýkora, Jan - Kubišta, Jiří - Pinkas, Jiří
    TITANOCENE AND ansa-TITANOCENE COMPLEXES BEARING 2,6-BIS(ISOPROPYL)PHENOXIDE LIGAND(S). SYNTHESES, CHARACTERIZATION AND USE IN CATALYTIC DEHYDROCOUPLING POLYMERIZATION OF PHENYLSILANE.
    Collection of Czechoslovak Chemical Communications. Roč. 76, č. 1 (2011), s. 75-94 ISSN 0010-0765
    Grant CEP: GA ČR GA203/09/1574; GA AV ČR KAN100400701; GA MŠk(CZ) LC06070
    Výzkumný záměr: CEZ:AV0Z40400503; CEZ:AV0Z40720504
    Klíčová slova: titatium * metallocenes * polymerization
    Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
    Impakt faktor: 1.283, rok: 2011

    Aryloxychloro and bis(aryloxy) titanocenes of general formula L2TiCl2-x(OAr')(x) where L = eta(5)-C5H5 (x = 1 (1) and 2 (2)), L-2 = SiMe2(eta(5)-C5H4)(2) (x = 1 (3) and 2 (4)), and Ar' = 2,6-(CHMe2)(2)C6H3 were prepared by the reaction of corresponding titanocene dichloride with LiOAr' and characterized by spectroscopic methods and compound 3 by single crystal X-ray diffraction analysis. The bulky aryloxy ligand in 1 and 3 exerts a hindered rotation around the Ti-O bond on the H-1 NMR time scale, resulting in its dynamic behavior in CDCl3 solution. Variable temperature NMR measurements proved the rotation barrier in 3 (Delta G(298)(double dagger) = 13.9 +/- 0.3 kcal/mol) to be lower than that in 1 (Delta G(298)(double dagger) = 14.7 +/- 0.2 kcal/mol) as a consequence of the more open titanocene shell in the ansa-structure of 3.
    Trvalý link: http://hdl.handle.net/11104/0196465