| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2000: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1999: ¥2,200,000 (Direct Cost: ¥2,200,000)
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| Research Abstract |
Various hexapyridine dinucleating ligands and their dicopper complexes have been synthesized to obtain functional models to mimic the reversible O_2-binding and O_2-activation of type III copper proteins. On the basis of reactions and structures of the copper complexes, it is shown that the reaction of μ-η^2 : η^2-peroxodicopper complex as an active species of the type III proteins is directed by various factors, such as the Cu coordination geometry, the orientation of two Cu ions, the Cu-Cu distance, and the electronic effect of the nitrogen donor ligands. Furthermore, it is suggested that the Cu-Cu distance and the distortion of the Cu coordination geometry may be important in controlling the reversible O_2-binding of the μ-η^2 : η^2-peroxodicopper complex.
A thermally stable (μ-1, 2-peroxo) diiron (III) complex [Fe_2 (O_2)(O)(OAc)(L)](CF_3SO_3)(2){L : 1, 2-bis [2-(bis (2-pyridyl) methyl)-6-pyridyl]ethane} were isolated from the reaction of [Fe_2 (O)(OAc)_2 (L)](CF_3SO_3)_2 (1b) with H_2O_2 in MeCN in the presence of Et_3N.Compound 2 was characterized by elemental analysis, FAB MS, elctronic absorption, resonance Raman, and Mossbauer spectra. The spontaneous decomposition of 2 in MeCN monitored at 605 nm obeys good first-order kinetics with k=2.5x10^<-5> s^<-1> at 300 K (the half-life time τ_<1/2>=7.7 h), demonstrating that 2 is thermally stable. Upon addition of RCOCl (R=m-ClC_6H_4, CH_3, and CCl_3) in the presence of DMF (or DMA), 2 is activated to monooxygenate cyclohexene and cyclohexane to the corresponding alcohols and ketones.
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