Genre
- Journal Article
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.
Univ Prince Edward Isl, Dept Chem, Charlottetown, PE C1A 4P3, Canada. Mem Univ Newfoundland, Sir Wilfred Grenfell Coll, Dept Chem, Corner Brook, NF A2H 6P9, Canada.; Haines, RI, Univ Prince Edward Isl, Dept Chem, 550 Univ Ave, Charlottetown, PE (TRUNCATED)
DORDRECHT; SPUIBOULEVARD 50, PO BOX 17, 3300 AA DORDRECHT, NETHERLANDS
KLUWER ACADEMIC PUBL
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Source type: Electronic(1)
Language
- English
Subjects
- ORGANIC MIXTURES
- INITIAL STATE
- MEDIA
- MECHANISM
- Chemistry, Inorganic & Nuclear
- PEROXYDISULFATE
- TRANSITION-STATE SOLVATION
- ION