Kinetics and mechanism of the reaction of tetracobalt dodecacarbonyl with carbon monoxide under pressure |
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Authors: | György Bor Urs K. Dietler Piero Pino Anthony Poë |
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Affiliation: | Department of Industrial and Engineering Chemistry, Swiss Federal Institute of Technology (E.T.H.), CH-8092 Zurich Switzerland;Erindale College and the Department of Chemistry, University of Toronto, Mississauga, Ontario L5L 1C6 Canada |
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Abstract: | The kinetics of the reaction of tetracobalt dodecacarbonyl with carbon monoxide to form dicobalt octacarbonyl in n-hexane have been investigated over a wide range of temperature and CO pressure. The reaction is first order in [Co4(CO)12]; the order in [CO] changes between one (at low pressures and high temperatures) and two (at high pressures and low temperatures).Activation parameters have been estimated and a mechanism involving initial reversible breaking of one CoCo bond, followed by irreversible breaking of a second, is proposed. The first step involves concerted addition of CO while the second can proceed with or without such addition. |
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