Abstract
Tetrapodal pentadentate ligands occupy five coordination positions in a coordination octahedron, thereby providing the metal ion with a square-pyramidal “coordination cap”: In such complexes, all reactivity is focused on a single coordination site. The review highlights recent advances in the coordination chemistry of iron. With a variety of NN4 ligands, the concept is being used to model non-heme active sites in biomolecules. Tetraphosphane ligands (donor set: NP4) undergo, depending on the solvent, remarkably specific P–C bond activation reactions, which may be reversed under suitable conditions.

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