Ruthenium catalysis reductive coupling

The catalysis cycle comprises the following steps oxidative addition of H2 to the metal coordination of the benzothiophene in the 77 -mode hydride migration and, finally, elimination of dihydrobenzo[3]thiophene by reductive coupling of the hydride and dihydrobenzothienyl ligands (Scheme 73). Based on this, various ruthenium and rhodium complexes have been developed, which exibit good catalytic activity. 

Recently, Dong et al. reported a multicatalytic cascade reaction combining Pd, acid, and Ru catalysis [11]. By coupling palladium-catalyzed oxidation, acid-catalyzed hydrolysis, and ruthenium-catalyzed reduction, the elusive anti-Markovnikov olefin hydration was formally achieved, affording primary alcohols from waters and aryl-substituted terminal alkenes (Scheme 9.8). 

The strong interactions with metal ions extend to the use of metal-modified electrodes in electrocatalysis. Catalysis has been demonstrated with four systems. Chromium treatment results in as much as a 200 mV positive shift in the reduction peak for lO in acetate buffer This has been compared to the necessity for prior oxidation of the platinum electrode surface Ruthenium pretreatment of (SN), electrodes results in a catalytic current for the I / couple in phosphate buffer, pH 7.6. These electrodes also photoelectrochemically reduce protons to hydrogen at —0.05 V versus SCE in dilute sulfuric acid solution Molybdate treated electrodes have been used to electrochemically reduce acetylene at potentials of 1.5 V versus SCE in borate and hydroxide solutions. Iron treated electrodes show some ability to facilitate this reaction, but the rate is slower than with the molybdate treated electrodes... 

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