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http://140.128.103.80:8080/handle/310901/21107
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| Title: | 4- and 3-cyanopyridine-bridged binuclear complexes of pentacyanoferrate and pentaammineruthenium |
| Authors: | Huang, H.-Y., Chen, W.-J., Yang, C.-C., Yeh, A. |
| Contributors: | Department of Chemistry, Tunghai University |
| Date: | 1991 |
| Issue Date: | 2013-05-14T09:01:54Z (UTC)
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| Abstract: | The binuclear complexes (CN)5Fe(PyCN)Ru(NH3)5 - (III) (4- and 3-isomers) were prepared by the substitution reactions of Ru(NH3)5NCPy2+ on Fe(CN)5OH2 3-. Complexes III undergo nitrile hydrolysis to give mixed-valence species of the form (CN)5Fe(PyCONH)Ru(NH3)5 - (IV) (4- and 3-isomers) when they are subjected to chemical oxidations of 1 equiv of peroxydisulfate. The results of UV-vis, IR, and electrochemical data suggest that complexes IV belong to a valence-trapped formulation containing the localized oxidation states Fe(II) and Ru(III). Rate constants of formation and dissociation of III and IV were measured, and the values of kf (∼ 103 M-1 s-1) and kd (∼ 10-3 s-1) were consistent with kinetic results expected for the substitution of Fe(CN)5OH2 3- with the divalent ligands. The kinetics of the nitrile hydrolysis were investigated, and it was found that the oxidized binuclear complexes III hydrolyze at a faster rate than the corresponding mononuclear Ru(III) complexes. Cyclic voltammetry of IV shows that the oxidation proceeds in two one-electron steps corresponding to [III,L,III] + e ? [II,L,III] and [II,L,III] + e ? [II,L,II]. The 4-isomer-bridged binuclear complex IV exhibits an intervalence band at 645 nm with molar absorbance 5.70 × 102 M-1 cm-1 and a half-width of 5100 cm-1. The properties of the IT band are discussed on the basis of Hush's theory. ? 1991 American Chemical Society. |
| Relation: | Inorganic Chemistry
Volume 30, Issue 8, 1991, Pages 1862-1868 |
| Appears in Collections: | [化學系所] 期刊論文
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