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2015 Fiscal Year Final Research Report

Synthesis and reactivity of novel high-valent iron-oxo complexes

Research Project

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Project/Area Number 26620038
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Inorganic chemistry
Research InstitutionUniversity of Tsukuba

Principal Investigator

Kojima Takahiko  筑波大学, 数理物質系, 教授 (20264012)

Project Period (FY) 2014-04-01 – 2016-03-31
Keywords触媒・化学プロセス / 鉄錯体 / 構造と性質 / 酸化反応
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.

Free Research Field

錯体化学、光化学

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Published: 2017-05-10  

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