Formation of Trivalent Zirconocene Complexes from ansa-Zirconocene-Based Olefin-Polymerization Precatalysts: An EPR- and NMR-Spectroscopic Study
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Journal of the American Chemical Society
ISSN: 0002-7863
, E-ISSN: 1520-5126
|
| Вых. Данные |
Год: 2013,
Том: 135,
Номер: 9,
Страницы: 10710-10719
Страниц
: 10
DOI:
10.1021/ja403170u
|
| Авторы |
Lenton Taylor N.
1
,
Bercaw John E.
1
,
Panchenko Valentina N.
2
,
Zakharov Vladimir A.
2
,
Babushkin Dmitrii E.
2
,
Soshnikov Igor E.
2
,
Talsi Evgenii P.
2
,
Brintzinger Hans H.
3
|
| Организации |
| 1 |
Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125,
United States
|
| 2 |
Boreskov Institute of Catalysis, Russian Academy of Science, Siberian Branch, Pr. Lavrentieva 5, 630090 Novosibirsk, Russian Federation
|
| 3 |
Fachbereich Chemie, Universitat Konstanz, D-78457 Konstanz, Germany
|
|
Информация о финансировании (4)
|
1
|
Российский фонд фундаментальных исследований
|
10-03-91330
|
|
2
|
German Research Foundation
|
Me 1388/9-1
|
|
3
|
National Science Foundation
|
CHE-0639094
|
|
4
|
United States Department of Energy
|
DE-FG03-85ER13431
|
Reduction of Zr(IV) metallocenium cations with sodium amalgam (NaHg) produces EPR signals assignable to Zr(III) metallocene complexes. The chloro-bridged heterodinuclear ansa-zirconocenium cation [(SBI)Zr(μ-Cl)2AlMe2]+ (SBI = rac-dimethylsilylbis(1-indenyl)), present in toluene solution as its B(C6F5)4– salt, thus gives rise to an EPR signal assignable to the complex (SBI)ZrIII(μ-Cl)2AlMe2, while (SBI)ZrIII-Me and (SBI)ZrIII(μ-H)2AliBu2 are formed by reduction of [(SBI)Zr(μ-Me)2AlMe2]+ B(C6F5)4– and [(SBI)Zr(μ-H)3(AliBu2)2]+ B(C6F5)4–, respectively. These products can also be accessed, along with (SBI)ZrIII-iBu and [(SBI)ZrIII]+ AlR4–, when (SBI)ZrMe2 is allowed to react with HAliBu2, eliminating isobutane en route to the Zr(III) complex. Further studies concern interconversion reactions between these and other (SBI)Zr(III) complexes and reaction mechanisms involved in their formation.