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1H and13C NMR Studies of Cationic Intermediates Formed upon Activation of "Oscillating" Catalyst (2-PhInd) 2ZrCl2 with MAO, MMAO, and AlMe3/[CPh 3]+[B(C6F5)4]- Научная публикация

Журнал Organometallics
ISSN: 0276-7333 , E-ISSN: 1520-6041
Вых. Данные Год: 2007, Том: 26, Номер: 6, Страницы: 1536-1540 Страниц : 5 DOI: 10.1021/om0610694
Ключевые слова Catalyst activity; Catalysts; Conformations; Ligands; Nuclear magnetic resonance spectroscopy
Авторы Lyakin Oleg Y. 1 , Bryliakov Konstantin P. 1 , Semikolenova Nina V. 1 , Lebedev Artem Y. 2 , Voskoboynikov Alexander Z. 2 , Zakharov Vladimir A. 1 , Talsi Evgenii P. 1
Организации
1 G. K. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russian Federation
2 Moscow State University, Lomonosovsky Prospect 1, 113000, Moscow, Russian Federation

Информация о финансировании (1)

1 Российский фонд фундаментальных исследований 06-03-32700

Реферат: The conformationally dynamic unbridged metallocene (2-PhInd)2ZrCl2 (1-Cl) was activated with methylaluminoxane (MAO), modified methylaluminoxane (MMAO), and AlMe3/[CPh3]+[B(C6F5)4]-. The following ion pairs were characterized by 1H and 13C NMR:  [(2-PhInd)2Zr(μ-Me)2AlMe2]+[Me-MAO]- (III), [(2-PhInd)2Zr(μ-Me)2AlMe2]+[B(C6F5)4]- (III‘), [(2-PhInd)2Zr(μ-Me)2AlMeiBu]+[Me-MAO]- (IIIMeiBu), [(2-PhInd)2Zr(μ-Me)2AliBu2]+[Me-MAO]- (IIIiBuiBu), and [(2-PhInd)2ZrMe+···Me-MAO-] (IV). In the temperature range −50 to 20 °C, the rotation of indenyl ligands of complexes III, III‘, and IIIMeiBu is faster than the evaluated rate of propylene insertion, whereas for IIIiBuiBu the rate of indenyl ligand rotation is comparable to or slower than the rate of propylene insertion. The ion pair IIIiBuiBu demonstrates the fundamental possibility of the existence of intermediates with the “locked” conformation of 2-PhInd ligands in 1-Cl/MAO or 1-Cl/MMAO systems. For the catalytic system 1-Cl/MAO, both outer sphere ion pair III and inner sphere ion pair IV are present in the reaction solution at high [Al]MAO/[Zr] ratios. For the catalytic system 1-Cl/MMAO, the concentration of inner sphere ion pairs of type IV is much smaller (below the NMR detection limit), and only outer sphere ion pairs IIIMeiBu and IIIiBuiBu are observed.
Библиографическая ссылка: Lyakin O.Y. , Bryliakov K.P. , Semikolenova N.V. , Lebedev A.Y. , Voskoboynikov A.Z. , Zakharov V.A. , Talsi E.P.
1H and13C NMR Studies of Cationic Intermediates Formed upon Activation of "Oscillating" Catalyst (2-PhInd) 2ZrCl2 with MAO, MMAO, and AlMe3/[CPh 3]+[B(C6F5)4]-
Organometallics. 2007. V.26. N6. P.1536-1540. DOI: 10.1021/om0610694 WOS Scopus РИНЦ CAPlusCA OpenAlex
Даты:
Поступила в редакцию: 22 нояб. 2006 г.
Опубликована online: 17 февр. 2007 г.
Опубликована в печати: 1 мар. 2007 г.
Идентификаторы БД:
Web of science: WOS:000244591400030
Scopus: 2-s2.0-33947644814
РИНЦ: 13560033
Chemical Abstracts: 2007:177875
Chemical Abstracts (print): 146:422084
OpenAlex: W2008796772
Цитирование в БД:
БД Цитирований
Web of science 16
Scopus 20
РИНЦ 19
OpenAlex 20
Альметрики: