Inorganic Reaction Mechanisms [Vol 2] by J. Burgess, et al.,

By J. Burgess, et al.,

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This effect together with the removal of the trans ligand in the z direction away from the metal atom accounts for the decreasing rate in the series NH3 > en > trien, where the ligand field increases in the reverse order. A two-stage reduction of PtCls2- has been described 41 in which a fast complex formation is followed by a slower intramolecular redox step. Potentiometric evidence has been obtained for PtlV-Fell and (Fe11)2-Pt1v complexes which differ only slightly in stability constant. The kinetics of the reduction of the hydrated cobalt(rr1) ion have been re-examined 48 over a large temperature range, the rates being first order with respect to each reactant, - dln [Co"']/dt = {ko + ki/[H+])[Fex1] A marked acidity dependence is attributable to hydrolysis of the oxidant, the mechanism being described in terms of the reactions + (H,0),CoOH2+ + Fe" CO(H,O)~~+ Fe" + FeIrr Co2+ + Fe"' Co2+ '' > Both reaction rates are sensitive to the nature of the medium, and the rate constants are considered too large for a rate-determining substitution on the C o z or CoOH2+ ions.

R. Pladziewicz and J. H. Espenson, Inorg. , 1971, 10, 635. J . H. Espenson and R. J. Kinney, Inorg. , 1971,10, 376. 26 Inorganic Reaction Mechanisms steps to yield the octahedral Cr(H20),3+ion. The rate law is observed to be - d[Ta,Brlz2+]/dt = (k, + k~[HCr04-])[T~Br122+][H+][HCr04-] the second pathway (ks), second order in chromium(vr), being considered to involve the dichromate anion in the activated complex. The possibility of a two-electron transfer to CrtVcannot however be completely excluded.

In the reaction with (H3N),CoNOaa+and (H,N),CONO,~+-,there is interference from ligand reduction, although this is less marked in the case of the corresponding nitrito- and bi-oxalato-species. The reduction of the tetra-amminediaquocobalt(rr~)ion, ci~c-Co(NH,)~(H20)23+has been examined U3++ CO(NH,),(H,O),~+ +4H + Up++ Co2+ + 4NH4+ + 2H,O in acid solutions at various ionic Considerable care was taken in the purification of the cobalt complex and the variations in spectral characteristics of samples from various preparations have been noted.

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