| Budget Amount *help |
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2014: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2013: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2012: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
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| Outline of Final Research Achievements |
A series of (dimethyl)(aryl)platinum-manganese pentacarbonyl complexes, (4,4'-R2bpy)Me2(p-XC6H4)Pt-Mn(CO)5 were prepared by the simple metathetical reactions of the corresponding (dimethyl)(aryl)(nitrato)platinum(IV) species with sodium pentacarbonylmanganate. These complexes show absorption bands in the visible region, which are ascribed to MLCT band from the HOMO orbital based on Mn ainon to the LUMO assignable to empty π* orbital of the bpy ligand. Selective methyl group transfer reactions in these complexes are unexpectedly accelerated by the irradiation of the light with a wavelength of maximum absorption. A possible mechanism is speculated by the experimental results and theoretical calculations. Since the irradiation causes electron promotion from the HOMO to the LUMO, the excited state of the complex involves a triplet Mn(I) cation with a bpy radical anion ligand. Selective reductive elimination may take place from such an excited state.
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