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• W2004673847 abstract "Oxidations of the NADH analogues 10-methyl-9,10-dihydroacridine (AcrH2) and N-benzyl 1,4-dihydronicotinamide (BNAH) by cis-[RuIV(bpy)2(py)(O)]2+ (RuIVO2+) have been studied to probe the preferences for hydrogen-atom transfer vs hydride transfer mechanisms for the C−H bond oxidation. 1H NMR spectra of completed reactions of AcrH2 and RuIVO2+, after more than ∼20 min, reveal the predominant products to be 10-methylacridone (AcrO) and cis-[RuII(bpy)2(py)(MeCN)]2+. Over the first few seconds of the reaction, however, as monitored by stopped-flow optical spectroscopy, the 10-methylacridinium cation (AcrH+) is observed. AcrH+ is the product of net hydride removal from AcrH2, but hydride transfer cannot be the dominant pathway because AcrH+ is formed in only 40−50% yield and its subsequent oxidation to AcrO is relatively slow. Kinetic studies show that the reaction is first order in both RuIVO2+ and AcrH2, with k = (5.7 ± 0.3) × 103 M-1 s-1 at 25 °C, ΔH‡ = 5.3 ± 0.3 kcal mol-1 and ΔS‡ = −23 ± 1 cal mol-1 K-1. A large kinetic isotope effect is observed, kAcrH2/kAcrD2 = 12 ± 1. The kinetics of this reaction are significantly affected by O2. The rate constants for the oxidations of AcrH2 and BNAH correlate well with those for a series of hydrocarbon C−H bond oxidations by RuIVO2+. The data indicate a mechanism of initial hydrogen-atom abstraction. The acridinyl radical, AcrH•, then rapidly reacts by electron transfer (to give AcrH+) or by C−O bond formation (leading to AcrO). Thermochemical analyses show that H• and H- transfer from AcrH2 to RuIVO2+ are comparably exoergic: ΔG° = −10 ± 2 kcal mol-1 (H•) and −6 ± 5 kcal mol-1 (H-). That a hydrogen-atom transfer is preferred kinetically suggests that this mechanism has an equal or lower intrinsic barrier than a hydride transfer pathway." @default.
• W2004673847 created "2016-06-24" @default.
• W2004673847 creator A5037787121 @default.
• W2004673847 creator A5051492016 @default.
• W2004673847 date "2005-03-08" @default.
• W2004673847 modified "2023-10-18" @default.
• W2004673847 title "Oxidations of NADH Analogues by <i>cis</i>-[Ru^IV(bpy)₂(py)(O)]²⁺ Occur by Hydrogen-Atom Transfer Rather than by Hydride Transfer" @default.
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• W2004673847 doi "https://doi.org/10.1021/ic048170q" @default.
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