The synthesis of a novel, tridentate, redox non-innocent ligand framework, H2dpmaNCy will be summarized.  Upon metallation to late, biologically relevant first-row transition metal centers (M = Mn, Fe, Co, Cu), a conformational distortion occurs resulting in the formation of a triganol bypyrimidal metal center with a pseudo-planar, meridinal ligand framework.  Tautormerization positons pendant amines in the secondary coordination sphere of the metal center.  Upon exposure of this class of complexes to a strongly coordinating solvent, the coordination geometry of the metal center changes to octahedral, where two solvent molecules bind in the apical positions of the complex and a counter ion is now outer sphere.  Reactivity of the complexes (dafaNCy)M(X)2 (X = Cl, OTf) with bidentate, redox active ligands results in ligand reorganization of the ancillary framework, revealing a facial coordination geometry of the tridentate framework.  Synthesis and characterization of the aforementioned complexes will be explored.

Structural diversity of tridentate ligand platforms with secondary coordination spheres

248th National Meeting (2014)

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