title: Rhodium-Mediated Oxygenation of Nitriles with Dioxygen: Isolation of Rhodium Derivatives of Peroxyimidic Acids.
abstract: Dioxygen is used as the oxygenation agent in the rhodium-mediated conversion of nitriles into amides. The characterization of intermediate species and model compounds as well as isotope-labeling studies provided an insight into the reaction mechanism. The conversions of rhodium hydroperoxido or methylperoxido complexes with nitriles into metallacyclic rhodium-κ(2)-(N,O)-peroxyimidate compounds represent essential key steps. The former are accessible from a rhodium(III) peroxido complex and the latter represent rhodium derivatives of Payne's reagent (peroxyimidic acids).
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin (Germany).
authors.forename: Annemarie
authors.initials: A
authors.lastname: Bittner
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin (Germany). thomas.braun@chemie.hu-berlin.de.
authors.forename: Thomas
authors.initials: T
authors.lastname: Braun
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin (Germany).
authors.forename: Roy
authors.initials: R
authors.lastname: Herrmann
authors.affiliation: Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin (Germany).
authors.forename: Stefan
authors.initials: S
authors.lastname: Mebs
keywords: metallacycle; oxygenation; peroxyimidic acid; reaction mechanism; rhodium