Template synthesis and structures of apically functionalized iron(ii) clathrochelates

Template condensation of three nioxime or dichloroglyoxime molecules with monosubstituted boronic acids on an iron(ii) ion matrix afforded apically functionalized tris-nioximate clathrochelates and hexachloride precursors of apically-ribbed functionalized clathratochelates, respectively. The macrobicyclic tris-nioximates containing apical o-dimethoxyphenyl, p-bromophenyl, phenylethynyl, biphenylyl, 6-pyrimidinyl, or tert-butyl substituents and the dibenzothienyl-containing hexachloroglyoximate clathrochelate thus obtained were characterized by elemental analysis and IR, UV-Vis, ¹H and ¹³C NMR, ⁵⁷Fe Mössbauer and PD mass spectroscopies. The structures of o-dimethoxyphenyl- and phenylethynyl-containing iron(ii) tris-nioximates and the dibenzothienyl precursor were established by X-ray diffraction analysis.