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Complexation and hydrogenation of olefins by chlororuthenate (II) in aqueous acid solution King, Roy James
Abstract
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.
Item Metadata
Title |
Complexation and hydrogenation of olefins by chlororuthenate (II) in aqueous acid solution
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Creator | |
Publisher |
University of British Columbia
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Date Issued |
1973
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Description |
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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Genre | |
Type | |
Language |
eng
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Date Available |
2011-03-28
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Provider |
Vancouver : University of British Columbia Library
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Rights |
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.
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DOI |
10.14288/1.0060132
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URI | |
Degree | |
Program | |
Affiliation | |
Degree Grantor |
University of British Columbia
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Campus | |
Scholarly Level |
Graduate
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Aggregated Source Repository |
DSpace
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Rights
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.