Unravelling Structural Mysteries of Simple Organozinc Alkoxides.

Simple RZnOR' alkoxides are among the first known organozinc compounds, and widespread interest in their multifaced chemistry has been driven by their fundamental significance and potential applications including various catalytic reactions. Nevertheless, their chemistry in solution and in the solid state remains both relatively poorly understood and a subject of constant debate. Herein, the synthesis and structural characterization of long-sought structural forms, a roof-like trimer [(tBuZn) (μ-OC(H)Ph ) (μ -OC(H)Ph )] and a ladder-type tetramer [(PhZn) (μ-OC(H)Ph ) (μ -OC(H)Ph ) ], incorporating diphenylmethanolate as a model alkoxide ligand, are reported.

tert-Butyl(tert-butoxy)zinc hydroxides: hybrid models for single-source precursors of ZnO nanocrystals.

Alkylzinc alkoxides, [RZnOR']4, have received much attention as efficient precursors of ZnO nanocrystals (NCs), and their "Zn4O4 " heterocubane core has been regarded as a "preorganized ZnO". A comprehensive investigation of the synthesis and characterization of a new family of tert-butyl(tert-butoxy)zinc hydroxides, [(tBu)4 Zn4 (μ3-OtBu)x (μ3-OH)4-x], as model single-source precursors of ZnO NCs is reported. The direct reaction between well-defined [tBuZnOH]6 (16) and [tBuZnOtBu]4 (24) in various molar ratios allows the isolation of new mixed cubane aggregates as crystalline solids in a high yield: [(tBu)4 Zn4 (μ3-OtBu)3 (μ3-OH)] (3), [(tBu)4Zn4 (μ3-OtBu)2 (μ3-OH)2] (4), [(tBu)4 Zn4 (μ3-OtBu)(μ3-OH)3] (5).

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.

Probing secondary coordination sphere influence on the oxygenation of zinc alkyls: formation of a unique zinc peroxide species.

Reactions of ethylzinc derivatives of o-hydroxybiphenyl with O2 were investigated. The study revealed an essential role in the oxygenation process of intra-molecular interactions involving aromatic rings and provided a unique aryloxide (hydroxide) Zn8(OAr)8(OH)6(O2) cluster with an encapsulated peroxide species.