Ligand Effects on the [Cu(PhO)(PhOH)]<sup>+</sup> Redox Active Complex

Under gas phase conditions, the [Cu(PhO)(PhOH)]<sup>+</sup> complex is composed of copper(I), a phenoxy radical bound via the oxygen atom, and a phenol bound via the aromatic ring. Effects of additional ligand coordination on the molecular and electronic structure of the complex [Cu(PhO)(PhOH)]<sup>+</sup> are investigated by mass spectrometric and quantum chemical means for [Cu(PhO)L]<sup>+</sup> (L = H<sub>2</sub>O, CH<sub>3</sub>OH, tetrahydrofuran, NH<sub>3</sub>, pyridine, imidazole, 1,2-dimethoxyethylene, <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetramethylethylenediamine, pyrrole, and thiophene) and [Cu(PhO)(PhOH)L<sub><i>n</i></sub>]<sup>+</sup> (L = H<sub>2</sub>O, NH<sub>3</sub>, and 4-methylimidazole) models. The nature and number of additional ligands critically influences the spin distribution in the complex, which is sensitively reflected by the phenoxy CO stretching mode.