2015 Fiscal Year Final Research Report
Synthesis and reactivity of novel high-valent iron-oxo complexes
| Project/Area Number |
26620038
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| Research Category |
Grant-in-Aid for Challenging Exploratory Research
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| Allocation Type | Multi-year Fund |
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| Research Field |
Inorganic chemistry
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| Research Institution | University of Tsukuba |
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Principal Investigator |
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| Project Period (FY) |
2014-04-01 – 2016-03-31
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| Keywords | 触媒・化学プロセス / 鉄錯体 / 構造と性質 / 酸化反応 |
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| Outline of Final Research Achievements |
A macrocyclic tetraamide ligand (H4DTTM) was synthesized through a template reaction using a Ni(II) complex. An intermediate-spin Fe(III) complex with DTTM(4-) as a ligand, (NEt4)2[Fe(III)(DTTM)Cl] (1), was prepared and characterized by X-ray analysis and spectroscopic methods. Complex 1 showed 2-step reversible redox processes in CH3CN. The redox processes were monitored by absorption spectroscopy to observe different isosbestic points for the two steps. We also succeeded in the isolation and crystal structure determination of the 1-electron- and 2-electron-oxidized species, which were obtained by chemical oxidation reactions of 1. The 1-electron-oxidized species was revealed to be in the S = 1 spin state and the 2-electron-oxidized one exhibited temperature-dependent valence tautomerization.
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| Free Research Field |
錯体化学、光化学
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