2023 Fiscal Year Annual Research Report
光駆動型不斉還元触媒を指向した四面体型Chiral-at-metal錯体の創成
| Project/Area Number |
22KJ0852
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| Allocation Type | Multi-year Fund |
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| Research Institution | The University of Tokyo |
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Principal Investigator |
LIU Yuanfei 東京大学, 理学系研究科, 特別研究員(PD)
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| Project Period (FY) |
2023-03-08 – 2024-03-31
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| Keywords | chiral-at-metal / spontaneous resolution / conglomerate crystal / hydrogen bonds / carbon-carbon cleavage / nickel / cobalt |
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| Outline of Annual Research Achievements |
The racemic tetrahedral chiral-at-nickel(II) complex, [NiIIL(ClLi(thf)2)] was synthesized and well characterized. Crystallization via liquid-liquid diffusion at －18 °C caused spontaneous resolution, which separated S/R isomers into different conglomerate crystals. By examining crystal structure of crystals, I found that nickel complexes of the same configuration extended into chiral helix via weakly interacting hydrogen bonds. Then the chiral helix of the same handedness further extended into 3D superstructure, eventually forming conglomerate crystals.
The racemic tetrahedral chiral-at-cobalt(II) complex was synthesized and well characterized. During the ligand exchange trials, it was found that by mixing the cobalt complex, 1,2-(dinaphth-1-yl)-1,2-ethlenediamine, AgClO4 and heating at 50 °C for 24 h, 12% of 1-naphthylaldehyde was obtained (NMR yield). Also, upon crystallization, [CoIIL(1-naphthylaldehyde)] crystals were obtained. Compared with control experiments, this result indicated that carbon-carbon bond cleavage of the 1,2-diamine would take place in the presence of the cobalt complex.
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