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Polymers 2015, 7(12), 2611-2624; doi:10.3390/polym7121536

Metathesis Polymerization Reactions Induced by the Bimetallic Complex (Ph4P)2[W2(μ-Br)3Br6]

1
Department of Inorganic Chemistry, Faculty of Chemistry, University of Athens, Panepistimiopolis Zografou, Athens 15771, Greece
2
Laboratory of Bioinorganic Chemistry, Department of Chemistry, University of Crete, Voutes Campus, Heraklion 71003, Greece
3
Department of Industrial Chemistry, Faculty of Chemistry, University of Athens, Panepistimiopolis Zografou, Athens 15771, Greece
*
Authors to whom correspondence should be addressed.
Academic Editor: Changle Chen
Received: 8 November 2015 / Revised: 24 November 2015 / Accepted: 1 December 2015 / Published: 9 December 2015
(This article belongs to the Special Issue Metal-Mediated Polymer Synthesis)
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Abstract

The reactivity of the bimetallic complex (Ph4P)2[W2(μ-Br)3Br6] ({W 2.5 W}7+, a′2e3) towards ring opening metathesis polymerization (ROMP) of norbornene (NBE) and some of its derivatives, as well as the mechanistically related metathesis polymerization of phenylacetylene (PA), is presented. Our results show that addition of a silver salt (AgBF4) is necessary for the activation of the ditungsten complex. Polymerization of PA proceeds smoothly in tetrahydrofuran (THF) producing polyphenylacetylene (PPA) in high yields. On the other hand, the ROMP of NBE and its derivatives is more efficient in CH2Cl2, providing high yields of polymers. 13C Cross Polarization Magic Angle Spinning (CPMAS) spectra of insoluble polynorbornadiene (PNBD) and polydicyclopentadiene (PDCPD) revealed the operation of two mechanisms (metathetic and radical) for cross-linking, with the metathesis pathway prevailing. View Full-Text
Keywords: metathesis; ROMP; metal-metal bonds; tungsten metathesis; ROMP; metal-metal bonds; tungsten
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Chriti, D.; Grigoropoulos, A.; Raptopoulos, G.; Charalambidis, G.; Nikolaou, V.; Coutsolelos, A.G.; Pitsikalis, M.; Mertis, K.; Paraskevopoulou, P. Metathesis Polymerization Reactions Induced by the Bimetallic Complex (Ph4P)2[W2(μ-Br)3Br6]. Polymers 2015, 7, 2611-2624.

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