Formation of Trivalent Zirconocene Complexes from ansa-Zirconocene-Based Olefin-Polymerization Precatalysts: An EPR- and NMR-Spectroscopic Study | Sciact - CRIS-system of Boreskov Institute of Catalysis

Formation of Trivalent Zirconocene Complexes from ansa-Zirconocene-Based Olefin-Polymerization Precatalysts: An EPR- and NMR-Spectroscopic Study Full article

Journal

Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126

Output data

Year: 2013, Volume: 135, Number: 9, Pages: 10710-10719 Pages count : 10 DOI: 10.1021/ja403170u

Tags

Chlorine compounds; Organometallics; Positive ions; Spectroscopic analysis; Zirconium

Authors

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

Affiliations

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

Funding (4)

1	Russian Foundation for Basic Research	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.

Lenton T.N. , Bercaw J.E. , Panchenko V.N. , Zakharov V.A. , Babushkin D.E. , Soshnikov I.E. , Talsi E.P. , Brintzinger H.H.
Formation of Trivalent Zirconocene Complexes from ansa-Zirconocene-Based Olefin-Polymerization Precatalysts: An EPR- and NMR-Spectroscopic Study
Journal of the American Chemical Society. 2013. V.135. N9. P.10710-10719. DOI: 10.1021/ja403170u WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Mar 29, 2013
Published online:	Jul 10, 2013
Published print:	Jul 24, 2013

Web of science:	WOS:000322432400024
Scopus:	2-s2.0-84880842120
Elibrary:	20449268
Chemical Abstracts:	2013:904141
Chemical Abstracts (print):	159:229689
OpenAlex:	W2168136167

DB	Citing
Web of science	32
Scopus	34
Elibrary	33
OpenAlex	38