反芳香族B,N-カルベンσ配位子の開発と常磁性/アニオン性金錯体の合成と物性解明
| Project/Area Number |
21K05099
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Review Section |
Basic Section 34010:Inorganic/coordination chemistry-related
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| Research Institution | Hiroshima University |
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Principal Investigator |
SHANG RONG 広島大学, 先進理工系科学研究科(理), 助教 (70754216)
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| Project Period (FY) |
2021-04-01 – 2024-03-31
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| Project Status |
Completed (Fiscal Year 2023)
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| Budget Amount *help |
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2023: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2022: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2021: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
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| Keywords | main group ligand / redox active ligand / triplet ground state / electronic tuning / Aurate / Carbene / boron / 反芳香族σ配位子 / 有機遷移金属化学 / 機能性材料 |
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| Outline of Research at the Start |
本課題で研究対象とする分子群では，ホウ素と窒素からなる新規カルベン配位子のBNCを 鍵化合物として，反芳香族配位子による電子的、立体的なチューニング効果と，そこから導 かれる酸化還元特性との相関関係を明らかにする。近年，重原子であるがゆえの 特徴的な酸化還元挙動を示す金錯体に備わった触媒機能に注目が集まっており，光や熱によって誘起された電子移動過程の本質を解き明かすことは，また同時に錯体化学において普遍的一 般原理へと導くと期待される。未解明の金錯体を合成単離し， その物理的・化学的特性評価によって触媒能の向上や機能性材料としての基盤構築に貢献する。
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| Outline of Annual Research Achievements |
The interplay of aromaticity and antiaromaticity of conjugated π systems is a crucial design strategy for tuning electronic states and properties of molecules. This project developed 3 ligand systems for transition metals, whose structure permit potential orbital interactions between metal d orbitals and ligand π orbitals. We hypothesized that by changing the number of electrons in the M-L system through redox reactions, their electronic states and electronic properties can be tuned. Using this strategy, we were able to synthesis and characterize an anionic gold complexes bearing a 4π B, N-heterocyclic Carbene (BNC). The expected antiaromaticity and the inclusion of boron atoms in BNC results in its highly π-accepting and σ-donating abilities which are ideal to stabilize the unusual oxidation state. As a comparison, a π-donating B,N-containing heterocyclic Phosphide (BNP, 6π) ligand was synthesized. Its complexation on Au(I) will allowed a structural comparison to BNC-Au(I) complexes, which revealed both terminal and bridging binding mode of the phosphine ligand. Its redox behavior is under investigation. In addition, a CCC-type pincer based on a dipyridal-annulated N-heterocyclic carbene was also developed. It complexes to a Ir(I) precursor to form a homoleptic octahedral Ir(III) bispincer metallacycle through a series of facile deprotonation/C-H activation. A step-wise 4e oxidation allowed isolation of a racemic mixture of a chiral tricationic Ir(III) complex. Experimental data and computational analysis of this complex suggested a triplet ground state.
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Report
(3 results)
Research Products
(29 results)
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[Presentation] Bis(borane)-containing ligands: effects on bonding and reactivity2022
Author(s)
Rong Shang*, Souta Saito, Yoshitaka Kimura, Shu Furukawa, Leonardo I. Lugo-Fuentes, Kohei Susukida, Takumi Oishi, J. Oscar C. Jimenez-Halla, Joaquin Barroso-Flores, Yohsuke Yamamoto, Tsutomu Mizuta
Organizer
Singapore International Chemical Conference (SICC-11)
Related Report
Int'l Joint Research / Invited
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