Structure of tetraphenylarsonium tricyano-2,2 ...

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Title Structure of tetraphenylarsonium tricyano-2,2 ',6 ',2 ''-terpyridyl-ferrate(II), AsPh4[Fe-II(terpy)(CN)(3)]; and kinetics of oxidation of the complex anion by peroxodisulfate in water and in binary aqueous mixtures
Author(s) Robert I. Haines, D. Pieda, W. Goulding
Journal Transition Metal Chemistry
Date 1998
Volume 23
Issue 6
Start page 763
End page 769
Abstract The structure of the title compound has been determined by X-ray crystallography. The octahedral arrangement of ligands about the iron(II) centre is somewhat distorted, with the axial NC-Fe-CN bond angle being 174.3(4)degrees. The oxidation of the tricyano-2,2',6',2 '-terpyridylferrate(II) anion by the peroxodisulfate anion has been investigated in water and in binary aqueous mixtures. The reaction follows a second order rate law, with a second-order rate constant of 0.126 +/- 0.001 dm(3) mol(-1) s(-1) at 295.2 K. The enthalpy and entropy of activation in water are 51.3 +/- 1.8 kJ mol(-1) and -89 +/- 5 J K-1 mol(-1) respectively. The rate is retarded on addition of organic cosolvent. The transfer chemical potential of the initial state from water into mixed solvents has been determined from solubility measurements, and compared with the transfer potential of the transition state. Solvent effects on the reaction are discussed in terms of initial state versus transition state solvation.

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