Probing the Role of π Interactions in the Reactivity of Oxygen Species: A Case of Ethylzinc Aryloxides with Different Dispositions of Aromatic Rings toward the Metal Center

Ethylzinc derivatives of ortho-hydroxybiphenyl and 2,6-diphenylphenol that bear different nuclearity and dispositions of aromatic rings toward the metal center were synthesized and structurally characterized in the solid state and solution. This family of well-defined compounds was examined as a model system for the activation of dioxygen mediated by using complexes that feature lack of a redox-active metal center. Experimental and theoretical studies indicate an essential role in the oxygenation process of intramolecular interactions that involve aromatic subunits. Additionally, novel results for the oxygenation chemistry of alkylzinc compounds, including the isolation and structural characterization of the unique octanuclear aryloxide (hydroxide) compound Zn-8(OAr)(8)(OH)(6)(O-2) with an encapsulated peroxide species, are presented.