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Issue 25, 2013
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Isospecific polymerization of 1-hexene by C1-symmetric half-metallocene dimethyl complexes of group 4 metals with bidentate N-substituted iminomethylpyrrolyl ligands

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Abstract

Non-bridged half-metallocene dimethyl complexes of group 4 metals 2a–4a with an N-4-methoxyphenyl(iminomethyl)pyrrolyl ligand 1a were synthesized and characterized by NMR spectroscopy and X-ray analysis. Upon activation with [Ph3C][B(C6F5)4], these complexes became active catalysts for the polymerization of 1-hexene. A series of hafnium complexes with various N-substituents on the imine group of ligands 1b–1g were also prepared and applied as catalysts for 1-hexene polymerization. The activation parameters for the exchange process between the two methyl groups bound to the metal for Cp*MMe2(R-pyr) complexes were estimated by NMR shape analysis at various temperatures. The findings indicated that the transition state of the ligand flipping process might be associated with the isoselectivity of the polymerization reaction.

Graphical abstract: Isospecific polymerization of 1-hexene by C1-symmetric half-metallocene dimethyl complexes of group 4 metals with bidentate N-substituted iminomethylpyrrolyl ligands

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Publication details

The article was received on 17 Oct 2012, accepted on 21 Nov 2012 and first published on 21 Nov 2012


Article type: Paper
DOI: 10.1039/C2DT32481D
Citation: Dalton Trans., 2013,42, 9120-9128
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    Isospecific polymerization of 1-hexene by C1-symmetric half-metallocene dimethyl complexes of group 4 metals with bidentate N-substituted iminomethylpyrrolyl ligands

    T. Yasumoto, K. Yamamoto, H. Tsurugi and K. Mashima, Dalton Trans., 2013, 42, 9120
    DOI: 10.1039/C2DT32481D

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