Proceedings of the National Academy of Sciences of the United States of America
Mass spectrometry, Transient intermediates, C-H oxidation, Catalysis
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.
Perry, Richard H.; Cahill, Thomas J. III; Roizen, Jennifer L.; Du Bois, Justin; and Zare, Richard N., "Capturing Fleeting Intermediates in a Catalytic C-H Amination Reaction Cycle" (2012). Chemistry and Physics Faculty Articles. 197.