Development of coordinatively unsaturated first row transition metal complexes bearing the multiple organosilyl ligands

2019 Fiscal Year Final Research Report

• Project/Area Number: 16H04120
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: The University of Tokyo
• Principal Investigator: Sunada Yusuke 東京大学, 生産技術研究所, 准教授 (70403988)
• Project Period (FY): 2016-04-01 – 2020-03-31
• Keywords: ケイ素 / 第一周期遷移金属 / 配位不飽和 / 高反応性活性種 / 触媒機能 / 還元 / 脱水素化

Outline of Final Research Achievements

Synthesis of coordinatively unsaturated complexes is one of the straightforward way to develop the highly active transition metal catalysts. We have recently described that the introduction of the organosilyl ligands to the metal centers effectively contribute to stabilize the coordinatively unsaturated complexes. In this project, we focused on the synthesis of coordinatively unsaturated first-row transition metal complexes based on the use of organosilyl ligands, and application of the obtained complexes as the catalysts. We found that introduction of chelating organosilyl ligand as well as silyl anion is the efficient synthetic methods to construct the coordinatively unsaturated first-row transition metal complexes such as iron in a simple manner. In addition, high catalytic performance of the obtained complexes was also revealed in some catalytic reactions including hydrosilylation, hydrogenation, and reductive silylation of dinitrogen.

Free Research Field

有機金属化学

Academic Significance and Societal Importance of the Research Achievements

触媒的な物質合成においては、従来はパラジウムや白金などの貴金属化合物が触媒として用いられてきた。一方、鉄などの第一周期遷移は安価で入手容易な金属であるが、貴金属類と異なり触媒としての機能は非常に限定的であった。本研究では、鉄などに対し複数のケイ素配位子を導入することで、配位不飽和錯体を簡便に合成可能であり、また得られた錯体が、従来は貴金属触媒により実現されていた様々な触媒反応を達成できることを見出した。すなわち、鉄に対し貴金属と類似の触媒機能を付与する手法を開発し、貴金属を用いない触媒的物質合成に向けた方法論を開拓した。