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An In‐Depth Look at the Reactivity of Non‐Redox‐Metal Alkylperoxides
Author(s) -
Pietrzak Tomasz,
Justyniak Iwona,
Kubisiak Marcin,
Bojarski Emil,
Lewiński Janusz
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201904380
Subject(s) - chemistry , alkoxide , zinc , zinc hydroxide , redox , alkyl , carboxylate , reactivity (psychology) , homolysis , ligand (biochemistry) , metal , inorganic chemistry , hydroxide , photochemistry , polymer chemistry , organic chemistry , catalysis , radical , medicine , biochemistry , alternative medicine , receptor , pathology
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 Et 2 Zn to form a zinc alkoxide. Upon treatment of the zinc ethylperoxide with Et 2 Zn, 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.