| Budget Amount *help |
¥16,510,000 (Direct Cost: ¥12,700,000、Indirect Cost: ¥3,810,000)
Fiscal Year 2016: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Fiscal Year 2015: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2014: ¥9,360,000 (Direct Cost: ¥7,200,000、Indirect Cost: ¥2,160,000)
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| Outline of Final Research Achievements |
We clarified mechanism of dioxygen activation by diiron complex on the basis of resonance Raman and electronic absorption spectral studies, detailed kinetic studies, DFT calculations, kinetic isotope effect (KIE), and catalytic oxidation of alkane. The rate constants increased proportionally to the substrate concentration in low substrate concentration. In high substrate concentration, however, the rate constants converge to the same value regardless of the kind of substrate. This is explained by a two-step mechanism, where anti-oxodioxodiiron(IV) is formed via syn-to-anti transformation of the syn-dioxo form, and reacts with substrate as the oxidant. The anti-dioxo form is 620-fold more reactive in the C-H bond cleavage of ethylbenzene than the most reactive diiron system reported so far. The KIE with toluene/D8-toluene is 95 at -30°C, and the largest in diiron systems reported so far. The diiron complex efficiently catalyzes the oxidation of various alkanes with H2O2.
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