Chemical Implications of Incompatible Ligand versus Metal Coordination Geometry Preferences

Binding an electron deficient pincer ligand which strongly dictates planar, mer stereochemistry, to a metal which prefers tetrahedral structure, e.g., d10 CuCl, is explored for possible intramolecular redox chemistry. Experiment shows that the pincer ligand 2,2′-bis-tetrazinyl pyridine, btzp, forms a complex (btzp)­CuCl which is a chloride-bridged polymer in the solid state, hence with 20 valence electrons around copper. DFT calculations show that even the monomer has nonplanar copper with the tetrazinyl nitrogen lone pairs somewhat misdirected away from copper, with long Cu/N bonds, in a singlet ground state; 13.9 kcal/mol less stable is a triplet, whose electronic structure shows one electron from the ground state Cu­(I) has been transferred to a pincer π* orbital. Outer sphere electron transfer to (btzp)­CuCl yields (btzp)Cu where the added electron has gone into the pincer, to leave a ligand-centered radical, characterized by EPR, chemical reactivity, and X-ray photoelectron spectroscopy.