title: Capturing fleeting intermediates in a catalytic C-H amination reaction cycle.
abstract: We have applied an ambient ionization technique, desorption electrospray ionization MS, to identify transient reactive species of an archetypal C-H amination reaction catalyzed by a dirhodium tetracarboxylate complex. Using this analytical method, we have detected previously proposed short-lived reaction intermediates, including two nitrenoid complexes that differ in oxidation state. Our findings suggest that an Rh-nitrene oxidant can react with hydrocarbon substrates through a hydrogen atom abstraction pathway and raise the intriguing possibility that two catalytic C-H amination pathways may be operative in a typical bulk solution reaction. As highlighted by these results, desorption electrospray ionization MS should have broad applicability for the mechanistic study of catalytic processes.
authors.affiliation: Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA.
authors.forename: Richard H
authors.initials: RH
authors.lastname: Perry
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Cahill
authors.forename: Jennifer L
authors.initials: JL
authors.lastname: Roizen
authors.forename: Justin
authors.initials: J
authors.lastname: Du Bois
authors.forename: Richard N
authors.initials: RN
authors.lastname: Zare