Inorganic reaction mechanisms. vol. 7. Review of the by Royal Society of Chemistry

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Ll It is suggested that the first of the two terms in each corresponds to an outer-sphere pathway; this is borne out by a correlation of the rates of these and 110 J. -K. Heh and E. S . Could, Inorg. , 1978, 17,3142. M. Hery and K. Wieghardt, Znorg. , 1978, 17, 1130. r. spectra. Intramolecular electron-transfer rates have been measured. 'l* The incorporation of a reducible pyridine-type function in the carboxylato-penta-ammine series leads to a marked rate enhancement, even when there is no conjugated bond system linking the pyridine ring to the cobaltY1l5 * Strictly speaking, the intermediates in the CrII reductions are the CrIII adducts of these complexes.

E. + , by luminescence quenching experiments (cf. Section 4 below). Quenching rate constants for the cobalt complexes are similar to those of the free organic ligands, and it is noteworthy that some at least of the latter give transient radical species as products. A chemical mechanism is proposed, but attempts to detect the intermediate were unsuccessful. 116 Chemical mechanisms are thought to be involved in reactions of various complexes of the type [Co(NH,),(0,CC,H3NC0NH,)12+ with Cr2+,lo9but not with Cu+,ll0 and in reactions of complexes of the type [CO(NH,)~(O,CC,H,(R)NO~}]~+ with V2+but not with [ R U ( N H & ] ~ + .

104 M. Chou, C. Creutz, and N. Sutin, J . Am. Chem. , 1977, 99, 5615. 105 T. K. Keenan, J . Phys. , 1957,61, 1 117. 106 M. K. Loar, M. A. Sens, G . W. Loar, and E. S. Gould, Inorg. , 1978, 17, 330. A . B. Soares, R. S. Taylor, and A. G. Sykes, Znorg. , 1978, 17, 496. lol 102 24 Inorganic Reaction Mechanisms In aqueous solution the same reagents when mixed in the 1 : 1 ratio react rapidly, probably to give the same initial products, but the MoIV species then decomposes at a rate independent of IrIV or MoIII concentrations.

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