Reactivity of a Nickel(II) Bis(amidate) Complex with meta-Chloroperbenzoic Acid: Formation of a Potent Oxidizing Species

Teresa Corona, Florian F. Pfaff, Ferran Acuña-Parés, Apparao Draksharapu, Christopher J. Whiteoak, Vlad Martin-Diaconescu, Julio Lloret-Fillol, Wesley R. Browne, Kallol Ray, Anna Company

Research output: Contribution to journalArticlepeer-review

48 Scopus citations

Abstract

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).

Original languageEnglish (US)
Pages (from-to)15029-15038
Number of pages10
JournalChemistry - A European Journal
Volume21
Issue number42
DOIs
StatePublished - Oct 1 2015

Bibliographical note

Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords

  • high-valent metal species
  • nickel
  • oxidation
  • reactive intermediates
  • redox chemistry

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