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Issue 7, 2013
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Direct observation of a cationic ruthenium complex for ethylene insertion polymerization

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Abstract

We report here the first direct observation of a cationic ruthenium complex catalyzing ethylene insertion polymerization. An arene-tethered ruthenium complex (η6-C6H5(CH2)3SCH3RuCl2) (3) was synthesized and shown to be able to catalyze ethylene polymerization upon activation with AlMe2Cl. For mechanistic studies, we synthesized the homologous dimethylated η6-C6H5(CH2)3SCH3Ru(CH3)2 (4) complex, which upon activation with the Brookhart acid ([H(Et2O)2]+ [BAr′4]) was also active for ethylene insertion polymerization. 1H-NMR and mass spectrometry (MS) studies provide direct evidence for a ruthenium cationic [η6-C6H5(CH2)3SCH3Ru(oligomer)]+ complex as the active species during polymerization. This has unambiguously shown for the first time a ruthenium complex as the active species for catalyzing olefin insertion polymerization.

Graphical abstract: Direct observation of a cationic ruthenium complex for ethylene insertion polymerization

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Publication details

The article was received on 11 Mar 2013, accepted on 02 May 2013 and first published on 07 May 2013


Article type: Edge Article
DOI: 10.1039/C3SC50676B
Chem. Sci., 2013,4, 2902-2906

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    Direct observation of a cationic ruthenium complex for ethylene insertion polymerization

    M. A. Camacho-Fernandez, M. Yen, J. W. Ziller and Z. Guan, Chem. Sci., 2013, 4, 2902
    DOI: 10.1039/C3SC50676B

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