Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species
Herein, we report the formation of a highly reactive nickel-oxygen species that has been trapped following reaction of a NiII precursor bearing a macrocyclic bis(amidate) ligand with meta-chloroperbenzoic acid (HmCPBA). This compound is only detectable at temperatures below 250 K and is much more re...
| Autores: | , , , , , , , , , |
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| Tipo de documento: | artigo |
| Estado: | Versão publicada |
| Data de publicação: | 2015 |
| País: | España |
| Recursos: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositório: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:10256/13280 |
| Acesso em linha: | http://hdl.handle.net/10256/13280 |
| Access Level: | Acesso embargado |
| Palavra-chave: | Reaccions químiques Chemical reactions Níquel -- Oxidació Nickel -- Oxidation |
| Resumo: | Herein, we report the formation of a highly reactive nickel-oxygen species that has been trapped following reaction of a NiII precursor bearing a macrocyclic bis(amidate) ligand with meta-chloroperbenzoic acid (HmCPBA). This compound is only detectable at temperatures below 250 K and is much more reactive toward organic substrates (i.e., CH bonds, CC bonds, and sulfides) than previously reported well-defined nickel-oxygen species. Remarkably, this species is formed by heterolytic OO bond cleavage of a Ni-HmCPBA precursor, which is concluded from experimental and computational data. On the basis of spectroscopy and DFT calculations, this reactive species is proposed to be a NiIII-oxyl compound. A highly reactive nickel-oxygen species has been spectroscopically trapped after heterolytic OO bond cleavage during the reaction of a NiII precursor with meta-chloroperbenzoic acid (HmCPBA). This species is used to carry out the oxidation of different substrates, such as olefins, sulfides, and CH bonds (see scheme) |
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