Development of precisely designed metalloligands for new transition metal catalysis

2020 Fiscal Year Final Research Report

• Project/Area Number: 17H03019
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: Takaya Jun 東京工業大学, 理学院, 准教授 (60401535)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Keywords: 有機合成化学 / 有機金属化学 / 錯体化学

Outline of Final Research Achievements

We have successfully synthesized a series of palladium complexes having a Z-type, group 13 metalloligand utilizing 6,6''-bis(phosphino)-2,2':6',2''-terpyridine derivatives as an efficient scaffold for M-E bonds (E = Al, Ga, In). Systematic investigation revealed unique characteristics of the Al-metalloligand in both structure and reactivity, which exhibited the highest catalytic activity for hydrosilylation of CO2 ever reported (TOF = 19300 h-1). We have also achieved synthesis of an Ir complex having a pincer-type gallylene ligand through the complexation-induced reduction of GaIII by IrI utilizing the N,P-multidentate ligand. The pincer-type structure enabled various reactions at Ir with keeping the gallylene ligand intact. Furthermore, we also demonstrated that the Ga-Rh complex can be an efficient catalyst for hydrosilylation of nitriles to imine oxidation level. This is a highly useful method for the synthesis of oximes from nitriles.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

本研究では，独自に開発した遷移金属二核錯体が，二酸化炭素の超効率的固定化反応などにおける超効率的触媒として機能することを明らかにした。これは，省資源・省エネルギー型の有用物質合成を実現するものとして大きな意義を持つ。