An In‐Depth Look at the Reactivity of Non‐Redox‐Metal Alkylperoxides |
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Authors: | Tomasz Pietrzak Iwona Justyniak Marcin Kubisiak Emil Bojarski Janusz Lewiski |
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Institution: | Tomasz Pietrzak,Iwona Justyniak,Marcin Kubisiak,Emil Bojarski,Janusz Lewiński |
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Abstract: | 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. |
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Keywords: | Alkylgruppen Disauerstoff Oxygenierungen Peroxide Zink |
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