The limiting dissociative mechanism for substitution at thed
6 centres molybdenum(O), iron(II), and cobalt(III): Kinetics of substitution at the pentacyano-4-Cyanopyridineferrate(II) anion and at 4-cyanopyridinemolybdenum(I) pentacarbonyl |
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Authors: | Ezz-Eldin A Abu-Gharib Razak bin Ali Michael J Blandamer John Burgess |
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Institution: | (1) Chemistry Department, University of Leicester, LEI 7RH Leicester, UK;(2) Present address: Faculty of Science, Sohag, Egypt;(3) Present address: Chemistry Department, University of Technology, Gurney Road, Kuala Lumpur, Malaysia |
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Abstract: | Summary Rate constants are reported for reaction of the 4-cyanopyridine complexes Fe(CN)5(4CNpy)]3– and Mo(CO)5(4CNpy)] with a variety of incoming ligands, in aqueous methanol (40 vol % MeOH) and in toluene respectively, at 298.2 K (ambient pressure). The dependence of rate constants on the nature and concentration of the incoming ligand is discussed in terms of the operation of the limiting dissociative,D, mechanism for substitution; the operation of this mechanism here, and in analogous pentacyanoferrate(II), pentacarbonylmolybdenum(I), and penta- and tetra-cyanocobaltate(III) complexes is reviewed. The effect of pressure on rate constants for replacement of 4-cyanopyridine in Mo(CO)5(4CNpy)], in toluene solution at 298.2 K, indicates an activation volume of +3 cm3 mol–1. |
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