| 研究実績の概要 |
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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