Development of New Reactions Based on the Construction of Precisely Designed Multidentate Ligands

2020 Fiscal Year Final Research Report

• Project Area: Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
• Project/Area Number: 15H05800
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: Iwasawa Nobuharu 東京工業大学, 理学院, 教授 (40168563)
• Project Period (FY): 2015-06-29 – 2020-03-31
• Keywords: 有機合成化学 / 遷移金属錯体 / 金属ー金属結合

Outline of Final Research Achievements

By using 6,6 ”-bisphosphinoterpyridine ligands, we have successfully realized a general method for the synthesis of hetero-dinuclear metal complexes containing metal-metal bonds by sequentially introducing two different metals to the scaffold. In addition, we were able to accumulate a lot of knowledge about the structure and bonding of these complexes based on single crystal X-ray structure analysis and theoretical methods. Furthermore, by utilizing the characteristic properties of the prepared complexes, we have developed a highly efficient hydrosilylation of carbon dioxide and a selective reduction of aromatic nitriles. In the former reaction, the highest turnover frequency was achieved.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

従来の遷移金属触媒を用いる反応開発ではもっぱら金属を一つ持つ錯体が用いられてきた。本研究では、新しい配位子PNNNP型配位子を用いて順次金属を導入するという手法により、金属－金属結合を持つ異種二核金属錯体の汎用的な合成法を確立し、異種金属－金属間の結合に関し系統的に知見を得ることができた。これらの成果は金属－金属結合を持つ異種二核金属錯体の化学という新しい研究分野の発展に大きく寄与するものである。また、これによりこれまで困難とされていた反応や高効率的な反応を実現することができ、遷移金属錯体触媒を用いて有用な物質を合成する際に新たな可能性を提供することができた。