Aqueous polymerization of styrene promoted by water-soluble robust ruthenium hydride complexes

Seiji Ogo, Keiji Uehara, Tsutomu Abura, Yoshihito Watanabe, Shunichi Fukuzumi

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Aqueous polymerization of styrene in biphasic media (styrene/water) has been achieved by water-soluble robust mononuclear hydride complexes [(ν6-C6Me6)RuII(bpy)H] n(X) {[1]n(X), where X = SO4 (n = 2) or CF 3SO3 (n = 1), bpy = 2,2′-bipyridine}. The hydride complex [1]2(SO4) was synthesized from the reaction of an aqua complex [(ν6-C6Me6)RuII. (bpy)(H2O)](SO4) {2(SO4)} with a water-soluble hydrogen donor HCOONa in H2O in a pH range of 4-12 at 70-100°C. The structures of [1]2(SO4) and 1(CF3SO 3) were determined by X-ray analysis, 1H and 2H NMR, IR, and electrospray ionization mass spectrometry (ESI-MS). X-ray analysis has revealed that complex 1(CF3SO3) adopts a distorted octahedral geometry with the Ru atom coordinated by one ν6-C 6Me6 ligand, one bidentate bpy ligand, and one terminal hydrido ligand that occupies a bond position. Complex [1]2(SO 4) reacts with excess amounts of styrene in biphasic media to provide polystyrene in a 62% isolated yield for 8 h. The polydispersity (M w/Mn) of the obtained polystyrene is 1.8. The isolated yield of polystyrene shows a maximum around pH 8. The pH-dependence is similar to the pH-dependent formation of 1. Growing polymer intermediates [(C 6Me6)Ru(bpy){(C2H3)-(C 6H5)}nH]+ (n = 1-4) were directly observed by ESI-MS.

Original languageEnglish
Pages (from-to)3047-3052
Number of pages6
Issue number12
StatePublished - 7 Jun 2004


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