Abstract
The results of both the oxidation and reduction of the (Rh/sub 2/(bridge)/sub 4/)/sub 2//sup 6 +/ (bridge = 1,3-diisocyanopropane, n = 2,3,4) ion in acedic media at a rotating glassy carbon disk electrode are reported. It is interesting to speculate about the relationship between the extreme irreversibility of the oxidation-reduction reactions and the photochemical production of hydrogen gas from hydrogen ions which have been observed for the Rh/sub 4//sup 6 +/ system. Due to the high-energy requirement for the reduction of hydrogen ions to hydrogen gas via hydrogen atom intermediates and the related back-electron-transfer problem encountered in excited-state electron-transfer reactions, systems such as the (Rh/sub 2/(bridge)/sub 4/)/sub 2//sup 6 +/ system, which are capable of undergoing irreversible two-electron-transfer reactions, will have distinct advantages in the production of hydrogen gas from aqueous solutions. Clearly, systems which display normal behavior (i.e., undergo reversible one-electron transfers) are systems which are unlikely to be able to cause H-H bond formation since they will be unable to supply the second electron to complete the formation of the H/sub 2/ bond before a back-electron-transfer step regenerates hydrogen ions.
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