Simultaneous utilization of vacant and filled orbitals of group 13 element compounds in low oxidation state: novel reaction and photoelectronic property

2023 Fiscal Year Final Research Report

• Project/Area Number: 21H01915
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 33010:Structural organic chemistry and physical organic chemistry-related
• Research Institution: Nagoya University
• Principal Investigator: Makoto YAMASHITA 名古屋大学, 工学研究科, 教授 (10376486)
• Project Period (FY): 2021-04-01 – 2024-03-31
• Keywords: ホウ素 / アルミニウム / 求核性 / アニオン / 金属間結合

Outline of Final Research Achievements

In this study, we focused on “Control of Electronic States of Group 13 Single-Bonded Molecules with High Electron Acceptance and New Reactions”. As a result, we found (1) tetra(1-naphthyl)diborane could be synthesized and its emission in solution showed a maximum at much shorter wavelength than those of the previously reported tetra(o-tolyl)diborane, and (2) unsymmetrical dialumanes and trialumanes could be synthesized by using an originally developed Al anion reagent and it was found that they are easily reduced. In addition, we also focused on “Elucidation of the Reactivity of Diamino-Al Anions”. We demonstrated that Al atoms could be introduced to V and Sm center to form unprecedented V-Al and Sm-Al bonds which have never been reported. Their unique reactivity toward small molecules were also shown in this study.

Free Research Field

有機金属化学・有機典型元素化学

Academic Significance and Societal Importance of the Research Achievements

本研究により得られた13族元素間単結合分子が示す高い反応性は、原子軌道である空軌道の重なりによりLUMOがその大きさをコンパクトに保ったままエネルギー準位が低下した結果であることを見いだしている。これは高反応性分子を設計するための新たな指針になると考えられる。また、Al-Sc, Al-V, Al-Sm分子は未踏の金属間結合を含んでおり、その電子状態に対する理解は合金の無機化学における理解に対しても一般化することが可能となる。このように、本研究はの成果は基礎化学的に重要であり、分子化学の根幹に対して大きく寄与すると言えよう。