Solvent-dependent electronic dichotomy in zinc complexes with non-innocent ligands: divalent Zn(+II)vs. monovalent Zn(+I) forms

Abstract

The relative stabilities and the electronic structures of zinc complexes bearing non-innocent ligands, associated with various oxidation states, are examined in this computational study, with particular attention paid to the influence of solvent polarity, modeled by explicit, implicit, and hybrid solvation approaches. Notably, we show that the stabilities and the electronic configuration of both the divalent species, described as a Zn^(+II) center coordinated to a fully reduced ligand (dianion), and the monovalent Zn^(+I) species, described as a Zn^(+I) center bound to a one-electron reduced ligand (radical anion), as a biradical, are highly sensitive to the polarity of the solvent. This study underscores the importance of performing geometry optimizations within the solvation model and highlights the use of structural features and bonding analysis tools in elucidating electronic structures.