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Issue 30, 2016
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Isoprene polymerization mediated by vanadium-[ONNO] complexes

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A series of vanadium complexes bearing dianionic tetradentate amine-bisphenolate [ONNO] ligands, V([double bond, length as m-dash]O)X[ONNOMe] (X = Cl (1); OiPr (2)), VCl2[ONNOMe] (3) and V(OiPr)2[ONNOR] (R = Me (4), tBu (5), Cl (6)), displaying various electronic and steric properties have been prepared. The molecular structures of two of these complexes, namely V[ONNOR](OiPr)2 with R = tBu (5) or Cl (6), are reported. Activated with dialkylmagnesium, all complexes lead to modest isoprene homo-polymerization activities at 50 °C. Quantitative polymerizations were observed using 4 and 6 as pre-catalysts combined with AliBu3. The resulting polyisoprene microstructure was composed of ca. 70% 3,4 enchainments, the remaining 30% 1,4 enchainments being a mixture of cis and trans stereoisomers. 6 leads to a more active catalyst than 4. β-Hydride abstraction occurs during the reaction.

Graphical abstract: Isoprene polymerization mediated by vanadium-[ONNO] complexes

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Publication details

The article was received on 08 Jun 2016, accepted on 24 Jun 2016 and first published on 27 Jun 2016

Article type: Paper
DOI: 10.1039/C6DT02288J
Citation: Dalton Trans., 2016,45, 12069-12077
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    Isoprene polymerization mediated by vanadium-[ONNO] complexes

    Y. Phuphuak, F. Bonnet, L. Vendier, C. Lorber and P. Zinck, Dalton Trans., 2016, 45, 12069
    DOI: 10.1039/C6DT02288J

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