UBC Theses and Dissertations
Complexation and hydrogenation of olefins by chlororuthenate (II) in aqueous acid solution King, Roy James
The formation of 1:1 π-complexes between chlororuthenate(II) and a series of substituted ethylenes in aqueous hydrochloric acid solution is described. Kinetic studies of the complexation for maleic, acrylic and crotonic acid substrates are presented. The likely mechanism is a two step process involving an initial S[subscript]N¹ dissociation of a chlororuthenate(II) complex or complexes. The nature of the blue chlororuthenate(II) species is uncertain and this prevents resolution of some questions about the mechanism; however, observations on the behavior of the blue solutions and some suggestions as to their possible nature are given. Acrylic and crotonic acids are hydrogenated catalytically via the ruthenium(II) π-complexes. Crotonaldehyde and crotonitrile complexes of chlororuthenate(II) are not hydrogenated but undergo hydration and/or polymerization. Kinetic data for the hydrogenation of the organic acids fit a well established mechanism. The factors which influence reaction rates in the hydrogenation steps are thoroughly discussed.
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