Studies on the kinetics and mechanism of anation reactions of some six-coordinate complexes of chromium(III) in aqueous solution |
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| Authors: | Debabrata Banerjea Bidyut Chakravarti |
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| Affiliation: | Department of Chemistry, University College of Science, 92 Acharyay Prafulla Chandra Road, Calcutta 700009, India |
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| Abstract: | Rates of stepwise anation of cis-Cr(ox)2(H2O2)− with SCN−/N3−, Cr(acac)2(H2O)2+ with SCN− and Cr(atda)(H2O)2 with SCN− have been investigated in weakly acidic aqueous solutions. Rate constants, kI and kII for the two steps in each system, are composite as kx = kx0+kxX[X−] (x = I, II; X− = SCN−, N3−). These rate constants have been evaluated also as the corresponding ΔH≠ and ΔS≠ values. The results obtained and the plausible Id mechanism seem to suggest Cr---OOC bond dissociation (hence a strongly negative ΔS≠) generating the transition state in each system with outer-sphere association forming the precursor complex in the X− dependent paths. |
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| Keywords: | Kinetics and mechanism Anation reactions Chromium complexes Six-coordinate complexes |
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