Ligand Effects on the [Cu(PhO)(PhOH)]⁺ Redox Active Complex

Under gas phase conditions, the [Cu(PhO)(PhOH)]⁺ 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)]⁺ are investigated by mass spectrometric and quantum chemical means for [Cu(PhO)L]⁺ (L = H₂O, CH₃OH, tetrahydrofuran, NH₃, pyridine, imidazole, 1,2-dimethoxyethylene, N,N,N′,N′-tetramethylethylenediamine, pyrrole, and thiophene) and [Cu(PhO)(PhOH)L_n]⁺ (L = H₂O, NH₃, 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.