2014 Fiscal Year Final Research Report
Study on Visible Light Enhanced Selective Reductive Elimination in Heterodinuclear Complex
Project/Area Number |
24550070
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Research Category |
Grant-in-Aid for Scientific Research (C)
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Allocation Type | Multi-year Fund |
Section | 一般 |
Research Field |
Inorganic chemistry
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Research Institution | Tokyo University of Agriculture and Technology |
Principal Investigator |
KOMINE Nobuyuki 東京農工大学, 工学(系)研究科(研究院), 助教 (90302918)
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Project Period (FY) |
2012-04-01 – 2015-03-31
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Keywords | 可視光 / ヘテロ二核錯体 / 還元的脱離 |
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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Free Research Field |
有機金属化学、有機化学
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