RESUMO
Substitution-inert complexes such as Fe(CN)(6)(4-) are usually considered to react by outer-sphere electron transfer (ET) with most electron acceptors, including aryl diazonium ions (ZC(6)H(4)N(2)(+), where Z denotes a substituent on the benzene ring). However, in contrast to the conclusion drawn in a previous report ( J. Am. Chem. Soc. 1987 , 109 , 1536 - 1540 ), kinetic studies and identification of products from the reactions of 4-nitro- and of 4-methoxybenzenediazonium with an excess of Fe(CN)(6)(4-) show that this is not the case and that the reactions actually go via the formation of an adduct, a diazoisocyanide complex [ZC(6)H(4)N(2)(+) + Fe(CN)(6)(4-) --> ZC(6)H(4)N(2)(NC)Fe(CN)(5)(3-)]. The adduct decomposes heterolytically by expulsion of nitrogen either to form an isocyanide complex [ZC(6)H(4)N(2)(NC)Fe(CN)(5)(3-) --> ZC(6)H(4)(NC)Fe(CN)(5)(3-) + N(2)] or the 4-substituted benzonitrile via a ligand exchange [ZC(6)H(4)N(2)(NC)Fe(CN)(5)(3-) --> ZC(6)H(4)CN + Fe(CN)(5)(3-) + N(2)]. A competing homolytic decomposition resulting in an overall ET reaction occurs only to a minor extent, giving small amounts of Fe(CN)(6)(3-), ZC(6)H(5), and various organic compounds. In oxygenated solutions ZC(6)H(4)N(2)(NC)Fe(CN)(5)(3-) decomposes to Fe(CN)(6)(3-) and ZC(6)H(4)OH. The measurements with Fe(CN)(6)(4-) were supplemented by the study of the analogous reactions of Os(CN)(6)(4-), Mo(CN)(8)(4-), and W(CN)(8)(4-). The observation that isocyanide and even short-lived diazoisocyanide complexes are formed is in accordance with an inner-sphere mechanism. Further support of this conclusion comes from the observation that the slope of the activation-free energy plots for the reactions of NO(2)C(6)H(4)N(2)(+) and MeOC(6)H(4)N(2)(+) with the four metal cyanides is higher than that expected for an outer-sphere ET mechanism. The implication of these results are discussed in the context of the previous report (vide supra) on the extraction of the self-exchange reorganization energies for substituted benzenediazonium salts from their reactions with Fe(CN)(6)(4-) and decamethylferrocene. Our conclusion is that Marcus theory is not applicable in the interpretation of the measured rate constants, thereby also precluding a determination of such energies.
RESUMO
The stoichiometry and the kinetics of oxidation of the cyanide complexes M(CN)n4- (M = Fe(II), Ru(II), Os(II), Mo(IV), and W(IV)) by the peroxydisulfate ion, S2O8(2-), and by the much more strongly oxidizing fluoroxysulfate ion, SO4F-, were studied in aqueous solutions containing Li+. Reactions of S2O8(2-) with M(CN)n4- are known to be strongly catalyzed by Li+ and other alkali metal ions, and this applies also to the corresponding reactions of SO4F-. The primary reactions of S2O8(2-) and SO4F- have both been found to be one-electron processes in which the equally strong O-O and O-F bonds are broken. The primary reaction of S2O8(2-) consists of a single step yielding M(CN)n3-, SO4-, and SO42-, whereas the primary reaction of SO4F- comprises two parallel one-electron steps, one leading to M(CN)n3-, SO4-, and F- and the other yielding M(CN)n-1(2-), CN-, SO4- and F-. The relationship between the rate constants and the standard free energies of reaction for the Li+-catalyzed reactions of SO4F- and S2O8(2-) with M(CN)n(4-), and for the uncatalyzed reactions of S2O8(2-) with bipyridyl and phenanthroline complexes MLn2+ (M = Fe(II), Ru(II), and Os(II)) studied previously, suggests that the intrinsic barrier for all three sets of reactions is similar, i.e., unaffected by the Li+ catalysis, and that the electron transfer and the breakage of the O-O and O-F bonds are concerted processes.
