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The activation energy is also similar to that in water and is independent of tributyl phosphate concentration and pH. 195. The stoicheiometry may be represented by the equation 3[Fe(C,H,),] + HCr0; + 7H++ 3[Fe(C5H5),]+ + Cr3+ + 4H20 The side reactions, the oxidation of acetone by CrVI, which occurs if the medium is acidic, and the slow decomposition of ferrocene in acidified solutions of acetone, were overcome by reaction of a solution containing both CrV1and ferrocene but no perchloric acid in one reservoir of the stopped-flow apparatus with a solution of perchloric acid in aqueous aeetone.
R. Hyde, R. Davies, and A. G. S. Dalton, 1972, 1838. J. H. Espenson and T. R. Webb, Znorg. , 1972,11, 1909. Reactions Between Two Metal Complexes 13 concentrations of ions such as C1-, Br-, I-, and NCS-, the overall rate law in the presence of such ions (X-)being The small decrease in rate with acidity which is also observed may be due to medium effects. In perchlorate media, the product is [Cr(H20)6]3+, whereas in the presence of other anions a mixture of Cr3+and CrX2+is obtained. The mechanism consistent with these findings may be represented as [TaeBr,,]2t + Cr3+ [Ta,Br,#+ + CrX2+ [TaeBr12]3+ + Cr2+ In the thiocyanate reaction, however, both linkage isomers [CrNCSI2+and the less stable [CrSCNI2+appear to be produced and it may be that an ion pair of the type [Ta6Brl2I3f NCS- is formed where the thiocyanate ion could act as a bridging ligand, leading to the formation of the S-bonded CrIII product.
Rosovskii, A. K. Misyavichyus, and A. Yu. Prokopchik, Zhur. neorg. , 1972, 17, 420. J. P. Birk and S. V. Weaver, Znorg. , 1972, 11, 95. 35 Reactions Between Two Metal Complexes The hydrogen-ion dependence is consistent with the mechanism + V02+ HzO=VO(OH)+ VO(OH)+ [ F e ( b i ~ y ) ~ ] ~ + VO: V02+ H20 [Fe(bipy),l3+zV0b + + + + + + H+ K& H+ [Fe(bipy),12+ 2H+ [Fe(bipy)J2+ + + The results are in qualitative agreement with the corresponding reactions involving [Fe(phen),13+ as oxidant. The reaction with [Fe(phen)J3+has also been used to obtain information on the reactivity of the differing forms of the p-amido-~-peroxo-bis[bis(ethylenediamine)cobalt(~~~)] complex,81 which is known to exist in three configurations (15)-(17) (amine ligands omitted).