Syntheses and Reactivities of Silanimine- and Phosphasilene-coordinated Electron-deficient Complexes

2018 Fiscal Year Final Research Report

• Project/Area Number: 15K05443
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Hirosaki University
• Principal Investigator: Okazaki Masaaki 弘前大学, 理工学研究科, 教授 (20292203)
• Co-Investigator(Kenkyū-buntansha): 太田 俊 弘前大学, 理工学研究科, 助教 (20733132)
• Project Period (FY): 2015-04-01 – 2019-03-31
• Keywords: シライミン錯体 / ホスファシレン錯体 / 電子欠損錯体 / 反応場構築 / ルイス酸 / カルベニウムイオン

Outline of Final Research Achievements

Reaction of an electron-deficient silanimine-coordinated titanium complex with ketones yielded the insertion products between the titanium-silicon bond. In the reaction with 1,3-dimethyl-2-imidazolidinone, the unusual cleavage of the carbon-oxygen double bond has been achieved. We also synthesized the silanimine-bridged diruthenium complex, which reacted with carbon monoxide and isocyanides to give the products. The reaction can be explained by assuming 1,2-H-shift of the bridging hydrogen atom to the nitrogen atom and the Si-H reductive elimination. These reactions are potentially applicable to the coupling between hydroamine and dihydrosilane. The iridium complexes possessing phosphasilene and silanethione moieties were synthesized and uniquely characterized by X-ray diffraction study. Theses complexes were highly reactive toward polarized small molecules.

Free Research Field

有機金属化学

Academic Significance and Societal Importance of the Research Achievements

これまで遷移金属錯体触媒の多くでは、一連の反応は金属中心で進行することが仮定され、分子設計がなされてきた。一方、元素戦略的な観点からいうと、希少な遷移金属に頼ることなく、クラーク数の大きい主要族元素を反応活性点として触媒を設計できれば、持続可能な社会構築に寄与できる。本研究成果は、ケイ素、窒素、リン、硫黄、炭素といった主要族元素を用いて、将来的に触媒へと展開可能な反応場の構築を行った点で、学術的および社会的な意義は大きいといえる。