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, R. H., Cahill, T. J., Roizen, J. L., Du Bois, J., & Zare, R. N. (2012). Capturing Fleeting Intermediates in a Catalytic C-H Amination Reaction Cycle. Proceedings of the National Academy of Sciences of the United States of America, 109, (45), 18295 - 18299. https://doi.org/10.1073/pnas.1207600109. Retrieved from https://nsuworks.nova.edu/cnso_chemphys_facarticles/197