An in-depth look at non-redox-metal alkylperoxides’ reactivity

Tomasz Pietrzak , I. Justyniak , Marcin Kubisiak , Emil Bojarski , Janusz Lewiński

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.
Author Tomasz Pietrzak (FC / DCOC)
Tomasz Pietrzak,,
- Department Of Catalysis And Organometallic Chemistry
, I. Justyniak
I. Justyniak,,
-
, Marcin Kubisiak (FC / DCOC)
Marcin Kubisiak,,
- Department Of Catalysis And Organometallic Chemistry
, Emil Bojarski (FC / DCOC)
Emil Bojarski,,
- Department Of Catalysis And Organometallic Chemistry
, Janusz Lewiński (FC / DCOC) - Institute of Physical Chemistry Polish Academy of Sciences (IChF PAN), MNiSW [80] [Polska Akademia Nauk (PAN)]
Janusz Lewiński,,
- Department Of Catalysis And Organometallic Chemistry
Journal seriesAngewandte Chemie-International Edition, ISSN 1433-7851, (N/A 200 pkt)
Issue year2019
Vol25
No58
Pages8526-8530
Publication size in sheets0.5
Keywords in English alkyls dioxygen oxygenation peroxide zinc
Keywords in original language alkyls dioxygen oxygenation peroxide zinc
ASJC Classification1600 General Chemistry; 1503 Catalysis
Abstract in original languageOver 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.
DOIDOI:10.1002/anie.201904380
URL https://onlinelibrary.wiley.com/doi/full/10.1002/anie.201904380
Languageen angielski
File
2019-Angewandte_Chemie_International_Edition.pdf 1.46 MB
Score (nominal)200
Score sourcejournalList
ScoreMinisterial score = 200.0, 20-10-2019, ArticleFromJournal
Publication indicators Scopus SNIP (Source Normalised Impact per Paper): 2017 = 2.165; WoS Impact Factor: 2017 = 12.102 (2) - 2017=11.954 (5)
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