Synthesis and Structural Studies of Gallium(III) and Iron(III) Hemicryptophane Complexes

New gallium­(III) and iron­(III) endohedral complexes were obtained from a hemicryptophane ligand bearing suitable binding sites for octahedral metal coordination. The solid-state structures of the free host and of the complexes were determined by single-crystal X-ray diffraction analysis. The metal ion is linked to the hydrazone nitrogen and the phenolate oxygen atoms, yielding a distorted octahedral geometry around the encapsulated metal. The two isomorphous structures of the metal complexes reveal the exclusive formation of PΔ/MΛ enantiomeric pairs.本研究以带有适配八面体金属配位结合位点的半穴状配体（hemicryptophane ligand）为原料，成功制备得到三价镓（gallium(III)）与三价铁（iron(III)）的内包配合物。通过单晶X射线衍射分析（single-crystal X-ray diffraction analysis），解析了游离主体与该配合物的固态晶体结构。金属离子与腙氮原子及酚氧原子配位结合，使得被包埋的金属中心呈现扭曲八面体配位几何构型。该金属配合物的两种同晶结构证实，体系仅生成PΔ/MΛ对映异构体对（enantiomeric pairs）。