Alternatives to pyridinediimine ligands: syntheses and structures of metal complexes supported by donor-modified alpha-diimine ligands

This report describes the synthesis and characterization of metal halide complexes (M = Mn, Fe, Co) supported by a new family of pendant donor-modified alpha-diimine ligands. The donor (N, O, P, S) substituent is linked to the alpha-diimine by a short hydrocarbon spacer forming a tridentate, mer-coordinating ligand structure. The tridentate ligands are assembled from monoimine precursors, the latter being synthesized by selective reaction with one carbonyl group of the alpha-dione. While attempts to separately isolate tridentate ligands in pure form were unsuccessful, metal complexes supported by the tridentate ligand are readily synthesized in-situ, by forming the ligand in the presence of the metal halide, resulting in a metal complex which subsequently crystallizes out of the reaction mixture. Metal complexes with NNN, NNO, NNP and NNS donor sets have been prepared and examples supported by NNN, NNP and NNS ligands have been structurally characterized. In the solid state, NNN and NNP ligands coordinate in a mer fashion and the metal complexes possess distorted square pyramidal structures and high spin (S = 2) electronic configurations. Compounds with NNS coordination environments display a variety of solid state structures, ranging from those with unbound sulfur atoms, including chloride bridged and solvent ligated species, to those with sulfur weakly bound to the metal center. The extent of sulfur ligation depends on the donor ability of the crystallization solvent and the substitution pattern of the arylthioether substituent.