Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland.
Institute of Physical Chemistry, Polish Academy of Science, Kasprzaka 44/52, 01-224, Warsaw, Poland.
Angew Chem Int Ed Engl. 2019 Jun 17;58(25):8526-8530. doi: 10.1002/anie.201904380. Epub 2019 May 10.
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 Zn to form a zinc alkoxide. Upon treatment of the zinc ethylperoxide with Et 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.
在过去的 150 年中，人们对非氧化还原活性金属中心的金属有机化合物的氧化的机械途径以及形成的产物的性质产生了一定的误解。值得注意的是，人们普遍认为常见的金属烷氧化物的形成是由于自动氧化反应，其中母体金属烷基化合物通过氧转移反应被金属烷基过氧化物氧化。现在，利用一种定义明确的锌乙基过氧化物，其中包含β-二酮亚胺配体，所研究的过氧烷基化合物不会与母体金属烷基配合物以及 EtZn 反应，从而形成锌烷氧化物。当用 EtZn 处理锌乙基过氧化物时，有利于发生先前未观察到的配体交换过程。母体锌乙基过氧化物分解产物的锌氢氧化物羧酸酯的分离证明了后者对 O-O 键均裂的敏感性。
