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13C-NMR Study of Ti(IV) Species Formed by Cp*TiMe3 and Cp*TiCl3 Activation with Methylaluminoxane (MAO) Full article

Journal Journal of Organometallic Chemistry
ISSN: 0022-328X
Output data Year: 2003, Volume: 683, Number: 1, Pages: 23-28 Pages count : 6 DOI: 10.1016/S0022-328X(03)00232-8
Tags Half-titanocene catalysts; Polysterene; Methylaluminoxane; Cationic intermediates; NMR; EPR
Authors Bryliakov Konstantin P. 1,2 , Semikolenova Nina V. 1 , Zakharov Vladimir A. 1 , Talzi Evgenii P. 1,2
Affiliations
1 Boreskov Institute of Catalysis, Pr. Lavrentieva 5, 630090 Novosibirsk, Russia
2 Novosibirsk State University, ul. Pirogova 2, 630090 Novosibirsk , Russia

Abstract: Using 13C- and 1H-NMR spectroscopy, titanium(IV) species formed in the catalytic systems Cp*TiMe3/MAO and Cp*TiCl3/MAO (Cp*=C5(CH3)5) in toluene and chlorobenzene were studied within the temperature range 253–293 K and at Al/Ti ratios 30–300. It was shown that upon activation of Cp*TiMe3 with methylaluminoxane (MAO) mainly the ‘cation-like’ intermediate Cp*Me2Ti+←Me−Al(MAO) (2) is formed. Three types of titanium(IV) complexes were identified in Cp*TiCl3/MAO catalytic system. They are methylated complexes Cp*TiMeCl2 and Cp*TiMe2Cl, and the ‘cation-like’ intermediate 2. Complex 2 dominates in Cp*TiCl3/MAO system in conditions approaching to those of practical polymerization (Al/Ti ratios more than 200). According to the EPR measurements, the portion of EPR active Ti(III) species in the Cp*TiCl3/MAO system is smaller than 1% at Al/Ti=35, and is about 10% at Al/Ti=700.
Cite: Bryliakov K.P. , Semikolenova N.V. , Zakharov V.A. , Talzi E.P.
13C-NMR Study of Ti(IV) Species Formed by Cp*TiMe3 and Cp*TiCl3 Activation with Methylaluminoxane (MAO)
Journal of Organometallic Chemistry. 2003. V.683. N1. P.23-28. DOI: 10.1016/S0022-328X(03)00232-8 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
Submitted: Jan 28, 2003
Accepted: Mar 31, 2003
Published online: May 8, 2003
Published print: Oct 7, 2003
Identifiers:
Web of science: WOS:000185957300004
Scopus: 2-s2.0-0141493661
Elibrary: 13433936
Chemical Abstracts: 2003:772741
Chemical Abstracts (print): 140:28067
OpenAlex: W2054736482
Citing:
DB Citing
Web of science 39
Scopus 40
Elibrary 42
OpenAlex 39
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