Redox regulation based on the pH-dependent hydrolysis of 2-pyridinecarboxaldehyde coordinated to ruthenium(II)

Electrochemistry of proton-coupled redox reactions. Role of the electrode surface

“…In catalysis, metal oxo complexes that can be reduced by combinations of electrons and protons are attractive in developing catalysts that perform oxidations by hydrogen atom and hydride transfer (1). In molecular electronics, protonation potentially allows redox sites to serve as "switches" by trapping electrons in a particular redox site (2). i In biological systems, metalloenzymes, whose function involves the oxidation or reduction of a metal ion, may control the kinetics and thermodynamics of the redox step by mediating acid-base chemistry of a coordinated ligand (3).…”

Mechanism of oxidative dehydrogenation of alcohols co-ordinated to ruthenium

“…There are two commonly accepted alternative paths for this latter process. The first involves the intermediacy of a liguncl radical species, and this has been identified in studies of the oxidations of nickel(I1) complexes of a variety of macrocycles, [6][7][8] ( N C , H , C H , O H ) ] ~ + seemed likely. Two additional observations favour this hypothesis.…”

Bis[pyrrolyl Ru(ii)] triads: a new class of photosensitizers for metal–organic photodynamic therapy

“…Previously, we have shown that 2-formyl and 2-keto pyrroles can replace one of the 2,2′-bipyridyl (bpy) ligands in [Ru(bpy) 3 ] 2+ to form stable complexes under ambient conditions with MLCT states shifted as much as 1.52 eV relative to the parent complex, 67 building on work involving 2-formylpyridyl ligands that convert to their hydrate form upon complexation. 68 In our model mononuclear 2-formylpyrrolide complexes, continuous absorption out to 600 nm was achieved without the need for sterically-demanding diimines such as 2,2′-biquinoline (biq) that are known to lower the energies of both MLCT and MC states, leading to red-shifted absorption, but also photodissociation.…”