title: Access to Formally Ni(I) States in a Heterobimetallic NiZn System.
abstract: Heterobimetallic NiZn complexes featuring metal centers in distinct coordination environments have been synthesized using diimine-dioxime ligands as binucleating scaffolds. A tetramethylfuran-containing ligand derivative enables a stable one-electron-reducedS= 1/2 species to be accessed using Cp2Co as a chemical reductant. The resulting pseudo-square planar complex exhibits spectroscopic and crystallographic characteristics of a ligand-centered radical bound to a Ni(II) center. Upon coordination of a π-acidic ligand such as PPh3, however, a five-coordinate Ni(I) metalloradical is formed. The electronic structures of these reduced species provide insight into the subtle effects of ligand structure on the potential and reversibility of the NiII/Icouple for complexes of redox-active tetraazamacrocycles.
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA.
authors.forename: Christopher
authors.initials: C
authors.lastname: Uyeda
authors.affiliation: Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, 91125, USA.
authors.forename: Jonas C
authors.initials: JC
authors.lastname: Peters