Construction of in situ, time-resolved, and temperature-changeable spectrometry

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In order to elucidate the mechanisms for the oxygen activation, O-O bond cleavage, oxidation, and so on, which are carried out in non-heme enzymes, in situ-observable, time-resolved, and temperature-changeable electronic absorption spectrometer has originally been constructed, and the following aspects have been found out. (I) The dinuclear iron complex modified by non-covalent interaction groups such as hydrogen bonding and hydrophobic sphere as hemerythrin model has been newly prepared, which exhibits a reversible reaction with dioxygen. (ii) The copper complex that has forced the geometry to four-coordinate square-pyramidal has originally been prepared. The reaction of the complex with hydrogen peroxide exhibited the formation of strong Cu(II)-hydroperoxide complex, which furthermore showed higher reactivity for substrates, (iii) The copper complexes that has forced the geometry to four-coordinate tetrahedral has been prepared using a new TACH ligand, whose di-μ-oxo-dicopper complex … More showed the highest reactivity among the copper complexes reported hitherto. In order to elucidate the mechanisms for the oxygen activation, O-O bond cleavage, oxidation, and so on , which are carried out in non-heme enzymes, in situ-observable, time-resolved, and temperature-changeable electronic absorption spectrometer has originally been constructed, and the following aspects have been found out. (I) The dinuclear iron complex modified by non-covalent interaction groups such as hydrogen bonding and hydrophobic sphere as hemerythrin model has been newly prepared, which exhibits a reversible reaction with dioxygen. (ii) The copper complex that has forced the geometry to four-coordinate square-pyramidal has originally been prepared. The reaction of the complex with hydrogen peroxide exhibited the formation of strong Cu(II)-hydroperoxide complex, which furthermore showed higher reactivity for substrates, (iii) The copper complexes that has forced the geometry to four-coordinate tetrahedral has been prepared using a new TACH ligand, whose di-μ-oxo-dicopper complex showed the highest reactivity among the copper complexes reported hitherto. Less