Transition state control of 3d transition metal catalysts and application to catalyst design

2019 Fiscal Year Final Research Report

• Project/Area Number: 17KT0006
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Multi-year Fund
• Section: 特設分野
• Research Field: Transition State Control
• Research Institution: Kyoto University
• Principal Investigator: Kurahashi Takuya 京都大学, 工学研究科, 准教授 (50432365)
• Project Period (FY): 2017-07-18 – 2020-03-31
• Keywords: 3d遷移金属触媒 / 溶液EPR測定 / 溶液XAFS測定 / 理論化学計算 / スペクトルシミュレーション / 逆問題解析 / 機械学習 / サポートベクター回帰

Outline of Final Research Achievements

Transition metal elements, such as Fe, Ni, have strong electron localization and orientation in the 3d orbit and have low electronic polarizability. Therefore, in the reaction design, the ligand selection needs to be performed more strictly from the viewpoint of the so-called "spatial structure and electronic structure" than in the case of using the 4d or 5d transition metal elements. In this study, based on the results of structural analysis in solution phase spectroscopy, and catalytic reaction mechanism analysis was carried out by theoretical chemical calculation. Based on the findings, we have developed an asymmetric catalytic reaction utilizing 3d transition metal elements. The catalytic functions were elucidated by NCIPlot, NBO analysis, and CDA analysis in the transition state structure of TDTS.

Free Research Field

有機化学

Academic Significance and Societal Importance of the Research Achievements

元素戦略の視点から開発が求められている3d遷移金属触媒反応の革新と再発見に繋がる成果を得ることができた。SPring-8での溶液XAFS測定や分子軌道法による理論化学計算を駆使することにより、触媒反応の遷移状態構造の設計が可能であることを示した。さらに、鉄やニッケルなどの3d遷移金属を活用する新規触媒反応の開発をおこない、その反応機構や触媒機能の解析を達成した。