Outer-sphere mechanisms hydrogenation using

NMR and UV-visible techniques have been used in the characterization of intermediates in the [Fe (edta)]" -promoted decomposition of hydrogen peroxide7 Fe complexes of edta, nta, and dtpa react with FISOs by an inner-sphere one-electron transfer mechanism with transient production of S04, in contrast to Cu, which reacts by an outer-sphere mechanism to give S04 and hydroxy radicalsFe -edta redox properties are relevant to Fe /Cu /H202 systems. ... 

Scheme 10. Concerted outer-sphere mechanism for the transfer hydrogenation using the Ru(r 6-arene)TsDPEN complex.

Asymmetric hydrogenation (Section 9.3) of C=C, C=0, and C=N bonds is widely employed with numerous catalysts. The example shown in Eq. 14.20 uses a Noyori catalyst that is believed to operate by an outer-sphere mechanism of Section 9.3 with transfer of H from the metal to carbonyl carbon and H+ from the amino hgand to the carbonyl oxygen, the carbonyl substrate not being directly coordinated to the metal. 

The reaction [Mn04] +[W(CN)gl is presumably outer-sphere in the ratedetermining steps. The hydrogen ion dependence is consistent with the two-path mechanism shown in equations (106)—(108). Using a literature value of the two... 

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