(Alkene)(peroxo) complexes are possible intermediates in catalytic and stoichiometric oxygenation of alkenes by dioxygen at rhodium and iridium, but they have not been observed in these reactions thus far. Some unreactive examples are known, yet only very few are well characterized. In the course of our studies with IrI-alkene complexes of dialkyldiarylguanidinato(1�) ligands, we have now identified such an (alkene)(peroxo) complex as an intermediate in the reaction of [Ir{PhNC(NMe2)NPh}(cod)] with O2 (cod = 1,5-cyclooctadiene). The new intermediate was characterized by one- and two-dimensional NMR as well as IR spectroscopy. Initial reactivity studies suggest that the intermediate undergoes alkene oxygenation upon decay.

Evidence for a reactive (alkene)(peroxo)iridium(III) complex

243rd National Meeting (2012)

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