ansa-Titanocene Catalysts for α-Olefin Polymerization. Syntheses, Structures, and Reactions with Methylaluminoxane and Boron-Based Activators | Sciact - CRIS-system of Boreskov Institute of Catalysis

ansa-Titanocene Catalysts for α-Olefin Polymerization. Syntheses, Structures, and Reactions with Methylaluminoxane and Boron-Based Activators Full article

Journal

Organometallics
ISSN: 0276-7333 , E-ISSN: 1520-6041

Output data

Year: 2005, Volume: 24, Number: 5, Pages: 894-904 Pages count : 11 DOI: 10.1021/om0492496

Tags

CRYSTAL-STRUCTURES; METALLOCENE DERIVATIVES; MOLECULAR-STRUCTURE; PROPYLENE POLYMERIZATIONS; BRIDGED COMPLEXES; ZIRCONOCENE; TITANIUM; REACTIVITY; ZIRCONIUM; RESONANCE

Authors

Bryliakov Konstantin P. ^1,2 , Babushkin Dmitrii E. ^1,2 , Talsi Evgenii P. ^1,2 , Voskoboynikov Alexander Z. ³ , Gritzo Holger ⁴ , Schröder Lars ⁴ , Damrau Hans-Robert H. ⁴ , Wieser Ulrich ⁴ , Schaper Frank ⁴ , Brintzinger Hans H. ⁴

Affiliations

1	Boreskov Institute of Catalysis, Russian Academy of Sciences
2	Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk, Russian Federation
3	Department of Chemistry, Moscow State University, Lomonosovsky Prospect 1, Moscow 113000
4	Fachbereich Chemie, University of Konstanz, D-78457 Konstanz, Germany

Funding (2)

1	International Association for the Promotion of Co-operation with Scientists from the New Independent States of the Former Soviet Union	00-841
2	University of Konstanz

The racemic isomers of C2H4(1-Ind)2TiCl2 and Me2Si(2-Me-Benzind)2TiMe2 were synthesized and structurally characterized. Reactions of these and related ansa-titanocene complexes with methylaluminoxane or with the cationizing reagent [CPh3]+[B(C6F5)4]-/Al2Me6 were monitored by UV/vis, 1H NMR, and EPR methods. Under conditions approaching those typically used in olefin polymerizations, heterobinuclear cations of the type [DianTiIV(μ-Me)2AlMe2]+ (with Dian = bridged ligand dianion) dominate in each of these reaction systems, which catalyze the polymerization of propene at temperatures below ambient. Above 0 °C, these cations are reduced, mainly to neutral heterobinuclear species DianTiIII(μ-Me)2AlMe2, which appear to be inactive with regard to polymerization catalysis. In the absence of monomer, the main reducing agent appears to be ethyl aluminum admixtures in Al2Me6. Addition of monomer increases the rate of reduction rather drastically, probably via formation of titanium hydrides.

Bryliakov K.P. , Babushkin D.E. , Talsi E.P. , Voskoboynikov A.Z. , Gritzo H. , Schröder L. , Damrau H-R.H. , Wieser U. , Schaper F. , Brintzinger H.H.
ansa-Titanocene Catalysts for α-Olefin Polymerization. Syntheses, Structures, and Reactions with Methylaluminoxane and Boron-Based Activators
Organometallics. 2005. V.24. N5. P.894-904. DOI: 10.1021/om0492496 WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Sep 29, 2004
Published online:	Jan 27, 2005
Published print:	Feb 28, 2005

Web of science:	WOS:000227098200022
Scopus:	2-s2.0-20044388102
Elibrary:	13481131
Chemical Abstracts:	2005:71515
Chemical Abstracts (print):	142:336436
OpenAlex:	W1980045530

DB	Citing
Web of science	66
Scopus	69
Elibrary	68
OpenAlex	69