2023 Fiscal Year Annual Research Report
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 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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| Keywords | main group ligand / redox active ligand / triplet ground state |
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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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Research Products
(12 results)
