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• W1967583897 abstract "The mechanistic pathways of formation of the NADH-like [Ru(bpy)2(pbnHH)]2+ species from [Ru(bpy)2(pbn)]2+ were studied in an aqueous medium. Formation of the one-electron-reduced species as a result of reduction by a solvated electron (k = 3.0 × 1010 M−1 s−1) or CO2•− (k = 4.6 × 109 M−1 s−1) or reductive quenching of an MLCT excited state by 1,4-diazabicyclo[2.2.2]octane (k = 1.1 × 109 M−1 s−1) is followed by protonation of the reduced species (pKa = 11). Dimerization (k7a = 2.2 × 108 M−1 s−1) of the singly reduced protonated species, [Ru(bpy)2(pbnH•)]2+, followed by disproportionation of the dimer as well as the cross reaction between the singly reduced protonated and nonprotonated species (k8 = 1.2 × 108 M−1 s−1) results in the formation of the final [Ru(bpy)2(pbnHH)]2+ product together with an equal amount of the starting complex, [Ru(bpy)2(pbn)]2+. At 0.2 °C, a dimeric intermediate, most likely a π-stacking dimer, was observed that decomposes thermally to form an equimolar mixture of [Ru(bpy)2(pbnHH)]2+ and [Ru(bpy)2(pbn)]2+ (pH < 9). The absence of a significant kinetic isotope effect in the disproportionation reaction of [Ru(bpy)2(pbnH•)]2+ and its conjugate base (pH > 9) indicates that disproportionation occurs by a stepwise pathway of electron transfer followed by proton transfer." @default.
• W1967583897 created "2016-06-24" @default.
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• W1967583897 date "2008-03-18" @default.
• W1967583897 modified "2023-10-06" @default.
• W1967583897 title "Mechanism of Hydride Donor Generation Using a Ru(II) Complex Containing an NAD⁺ Model Ligand: Pulse and Steady-State Radiolysis Studies" @default.
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• W1967583897 doi "https://doi.org/10.1021/ic702139n" @default.
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