Progress in Inorganic Chemistry: Inorganic Reaction by John O, Edwards

By John O, Edwards

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C. Photochemical Decomposition A number of mononuclear complexes CoITI(NH3),(X)” undergo photochemical reactions at 370 nm (25, p. 657) to give CO~~’(NH,),(H,O)~ + + 40 A. G. SYKES AND J. A. WEIL and/or cobalt(II), depending on the ease of oxidation of the attached ligand X. The p-superoxo dicobalt ions are sensitive even to visible light (383), and detailed studies of the processes involved have recently been made. 1M) (21) and also in dilute perchloric acid (407,408), the photochemical decomposition reaction + ( N H J ) 5 C ~ .

13 volt) (42) as well as a strong reducing agent HO, -+ 0, + H f + e- The rapid decomposition of potassium superoxide KO, in the presence of water, with formation of hydrogen peroxide and evolution of oxygen, is consistent with (41) and (42). , reactions with Br(102) and V 0 2 (383) have been reported). The p-superoxobis[pentacyanocobalt(III)] complex is known to be reduced by iodide (179), but otherwise reactions of this and the p-amido-p-superoxobis[tetracyanocobalt(III)] complex (285) have not been studied in any detail.

Bridge has a tetrahedral bonding system. p(NH, 0,). Co", \\it11 the cobalt atoms in oxidation states 111 and IV. There are now grave doubts (283,395) whether any dicobalt ions with imido bridges exist, and it will be necessary to investigate the other ions postulated to be of this form (165,438) to confirm this. Both the ethylenediamine- and ammine-substituted p-amido-pperoxo dicobalt complexes ha\-e been shown to undergo protonation and isomerization reactions (283,284). Since the ethylenediamine complexes are someLvhat more stable, most of the quantitative work has been done with them.

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