Probing the Role of π Interactions in the Reactivity of Oxygen Species

Chemistry – a European Journal, 2014, 20, 5093–5096.


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

Łukasz Mąkolski,a Karolina Zelga,a Rafał Petrus,b Dominik Kubicki,a Piotr Zarzycki,c Piotr Sobota,*b Janusz Lewiński*ac

a Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland
b Faculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie St., 50-383 Wrocław, Poland
c Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

DOI: 10.1002/chem.201403851
First published online: 18 Sep 2014

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 Zn8(OAr)8(OH)6(O2) with an encapsulated peroxide species, are presented. chej2014pi

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