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Hydrogen bonds influence secondary coordination spheres around metal ions in many proteins. To duplicate these features of molecular architecture in synthetic systems, urea-based ligands have have been developed that create rigid organic frameworks when bonded to metal ions. These frameworks position hydro-gen bond donors proximal to metal ion(s) to form specific chem-ical microenvironments. Iron(II) and manganese(II) complexes with constrained cavities activate O(2), yielding M(III) (M(III) = Fe and Mn) complexes with terminal oxo ligands. Installation of anionic sites within the cavity assists the formation of complexes with M(II/III)-OH and M(III)-O units derived directly from water. Opening the cavity promotes M(mu-O)(2)M rhombs, as illustrated by isolation of a cobalt(III) analogue, the stability of which is promoted by the hydrogen bonds surrounding the bridging oxo ligands.
A. S. Borovik (Sat,) studied this question.