High Valent Metal Complex: the Characterization and Reactivity
| Project/Area Number |
17H03027
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (B)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Inorganic chemistry
|
|---|
| Research Institution | University of Tsukuba |
|---|
Principal Investigator |
|
|---|
| Project Period (FY) |
2017-04-01 – 2020-03-31
|
| Project Status |
Completed (Fiscal Year 2019)
|
| Budget Amount *help |
¥18,980,000 (Direct Cost: ¥14,600,000、Indirect Cost: ¥4,380,000)
Fiscal Year 2019: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2018: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2017: ¥11,440,000 (Direct Cost: ¥8,800,000、Indirect Cost: ¥2,640,000)
|
|---|
| Keywords | ルテニウム錯体 / 酸化反応機構 / 反応速度論 / 高原子価状態 / 触媒・化学プロセス |
|---|
| Outline of Final Research Achievements |
In this research, Ru(IV)-oxo and a unprecedented Ru(V)-imido complexes, which can act as reactive species in oxidation reactions, have been prepared and characterized. We have determined reorganization energies (lambda) of electron transfer (ET) and proton-coupled electron transfer (PCET) for Ru(IV)=O complexes for the first time to reveal that the lambda value of PCET is smaller than that of ET. We have also revealed a PCET oxidation process of a Ru(II)-NH3 complex and characterized a Ru(V)=NH complex spectroscopically. C-H oxidation by the Ru(V)=NH complex in acidic water was elucidated to involve hydride transfer from a substrate together with proton transfer from water.
|
| Academic Significance and Societal Importance of the Research Achievements |
本研究で得られた成果は、酸化活性種として盛んに研究されている高原子価金属―オキソ及び－イミド錯体の反応性の理解を深める上で、非常に重要である。Ru(IV)=O錯体の電子移動特性の解明は、それらが関与する水素移動反応がどのような駆動力で進行するかに重要な示唆を与える。また、前例ないRuV=NH錯体の水溶液中での反応性が、これまでに知られているRu(V)=NR錯体とは一線を画すものであり、RuV=NH錯体によるC-H酸化反応が、窒素原子の基質への移動を水素移動ではなく、溶媒からのプロトン移動が関与するヒドリド移動で進行することを見いだしたことは、関連する酸化反応の化学に大きなインパクトを与えた。
|
Report
(4 results)
Research Products
(136 results)
-
-
-
-
-
-
-
-
-
-
-
-
[Journal Article] Formation of a Ruthenium(V)-Imido Complex and the Reactivity in Substrate Oxidation in Water through the Nitrogen Non-Rebound Mechanism2019
Author(s)
Tomoya Ishizuka, Taichi Kogawa, Misaki Makino, Yoshihito Shiota, Kazuaki Ohara, Hiroaki Kotani, Shunsuke Nozawa, Shin-ichi Adachi, Kentaro Yamaguchi, Kazunari Yoshizawa, Takahiko Kojima
-
Journal Title
Inorganic Chemistry
Volume: 58
Issue: 19
Pages: 12815-12824
DOI
Related Report
Peer Reviewed / Int'l Joint Research
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
[Presentation] Gas Adsorption Properties of Hydrogen-Bonded Networks Consisting of Non-Planar Metalloporphyrins2018
Author(s)
MARCHI OGAWA, Bruno Kazuhiro; ISHIZUKA, Tomoya; KOTANI, Hiroaki; TABE, Hiroyasu; YAMADA, Yusuke; KOJIMA, Takahiko; ISHIZUKA, Tomoya; KOTANI, Hiroaki; TABE, Hiroyasu; YAMADA, Yusuke; KOJIMA, Takahiko
Organizer
日本化学会第98春季年会2018
Related Report
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
