In‐Depth Look at the Reactivity of Non‐Redox‐Metal Alkylperoxides

Angewandte Chemie International Edition, 2019, 58, 8526–8530.


An In‐Depth Look at the Reactivity of Non‐Redox‐Metal Alkylperoxides

Tomasz Pietrzak,a Iwona Justyniak,b Marcin Kubisiak,a Emil Bojarski,a Janusz Lewiński*ab

Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

DOI: 10.1002/anie.201904380.
First published online 12 Apr 2019

Over the past 150 years, a certain mythology has arisen around the mechanistic pathways of the oxygenation of organometallics with non‐redox‐active metal centers as well as the character of products formed. Notably, there is a widespread perception that the formation of commonly encountered metal alkoxide species results from the auto‐oxidation reaction, in which a parent metal alkyl compound is oxidized by the metal alkylperoxide via oxygen transfer reaction. Now, harnessing a well‐defined zinc ethylperoxide incorporating a β‐diketiminate ligand, the investigated alkylperoxide compounds do not react with the parent metal alkyl complex as well as Et2Zn to form a zinc alkoxide. Upon treatment of the zinc ethylperoxide with Et2Zn, a previously unobserved ligand exchange process is favored. Isolation of a zinc hydroxide carboxylate as a product of decomposition of the parent zinc ethylperoxide demonstrates the susceptibility of the latter to O−O bond homolysis.

Paper on the Publisher’s website