The Influence of Redox-Innocent Donor Groups in Tetradentate Ligands Derived from -Phenylenediamine: Electronic Structure Investigations with Nickel.

The continued development of redox-active ligands requires an understanding as to how ligand modifications and related factors affect the locus of redox activity and spin density in metal complexes. Here we describe the synthesis, characterization, and electronic structure of nickel complexes containing triaryl NNNN () and SNNS () ligands derived from -phenylenediamine. The tetradentate ligands in and were investigated and compared to those in metal complexes with compositionally similar ligands to determine how ligand-centered redox properties change when redox-active flanking groups are replaced with redox-innocent NMe or SMe. A derivative of in which the phenylene backbone was replaced with ethylene () was also prepared to interrogate the importance of -phenylenediamine for ligand-centered redox activity. Cyclic voltammograms collected for and revealed two fully reversible ligand-centered redox events. Remarkably, several quasi-reversible ligand-centered redox waves were also observed for despite the absence of the -phenylenediamine subunit. Oxidizing and with silver salts containing different counteranions (BF, OTf, NTf) allowed the electrochemically generated complexes to be analyzed as a function of different oxidation states using single-crystal X-ray diffraction (XRD), EPR spectroscopy, and S K-edge X-ray absorption spectroscopy. The experimental data are corroborated by DFT calculations, and together, they reveal how the location of unpaired spin density and electronic structure in singly and doubly oxidized salts of and varies depending on the coordinating ability of the counteranions and exogenous ligands such as pyridine.