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- W2951030137 abstract "The effect of high pressure on the rates of racemization and aquation of Ni(~hen)~~+ and Fe(phen)32+ (phen = 1,lOphenanthroline) in solution has been evaluated. Reactions of Fe(~hen)~'+ exhibit a significant retardation upon the application of pressure, with volumes of activation (AV) of +14.2 and +15.6 cm3 mol-' for racemization in 0.01 and 1.0 M aqueous HC1, respectively, while aquation in 1.0 M aqueous HC1 exhibits a AV of +15.4 cm3 mol-'. Possible mechanisms are considered, and a positive contribution to AP from excitation to a high-spin transition state, associated with a general Fe-N bond expansion, is proposed as a component of the mechanism for aquation and racemization. Reactions of Ni(phen)p show only a minor acceleration of rates upon the application of pressure with AV = -0.4 cm3 mol-' and AV = -1.5 cm3 mol-' for racemization in 0.01 and 1.0 M aqueous HC1, respectively, while aquation in 1.0 M aqueous HCI exhibits a AV of -1.2 cm3 mol-'. A common mechanistic pathway is favored since determined rates and enthalpies and entropies of activation as well as volumes of activation for aquation and racemization are very similar. A dissociative mechanism for release of a phen ligand with possible formation in the transition state of a high-spin four-coordinate species of reduced volume compared with the low-spin octahedral precursor is favored from analysis with AV data." @default.
- W2951030137 created "2019-06-27" @default.
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- W2951030137 date "1978-07-01" @default.
- W2951030137 modified "2023-09-24" @default.
- W2951030137 title "Volumes of activation for racemization and aquation of tris(1,10-phenanthroline) complexes of nickel(II) and iron(II) in solution" @default.
- W2951030137 cites W2083898826 @default.
- W2951030137 doi "https://doi.org/10.1021/ic50185a020" @default.
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