Chromium(v)-oxo and chromium(iii)-superoxo complexes bearing a macrocyclic TMC ligand in hydrogen atom abstraction reactions

Jaeheung Cho, Jaeyoung Woo, Jung Eun Han, Minoru Kubo, Takashi Ogura, Wonwoo Nam

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53 Scopus citations

Abstract

A Cr(v)-oxo complex bearing a macrocyclic TMC ligand, [Cr V(TMC)(O)(OCH3)]2+, was synthesized, isolated, and characterized by various physicochemical methods, including UV-vis, ESI-MS, resonance Raman, EPR and X-ray analysis. The reactivity of the Cr(v)-oxo complex was investigated in C-H and O-H bond activation reactions. The reactivity of a Cr(iii)-superoxo complex, [CrIII(TMC)(O2)(Cl)] +, was investigated in O-H bond activation reactions as well. By comparing reactivities of the Cr(iii)-superoxo and Cr(v)-oxo complexes under the identical reaction conditions, we were able to demonstrate that the Cr(iii)-superoxo complex is more reactive than the Cr(v)-oxo complex in the activation of C-H and O-H bonds. The present results provide strong evidence that under certain circumstances, metal-superoxo species can be an alternative oxidant for high-valent metal-oxo complexes in oxygenation reactions.

Original languageEnglish
Pages (from-to)2057-2062
Number of pages6
JournalChemical Science
Volume2
Issue number10
DOIs
StatePublished - Oct 2011

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