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Chemistry and Physics Faculty Articles
Document Type
Article
Publication Date
11-6-2012
Publication Title
Proceedings of the National Academy of Sciences of the United States of America
Keywords
Mass spectrometry, Transient intermediates, C-H oxidation, Catalysis
ISSN
0027-8424
Volume
109
Issue/No.
45
First Page
18295
Last Page
18299
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.
Additional Comments
Air Force Office of Scientific Research grant #: FA 9550-10-1-0235; Center for Molecular Analysis and Design at Stanford University grant #: 1123893-1-AABGE; NIH fellowship #: 5F32GM089033-02
NSUWorks Citation
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
DOI
10.1073/pnas.1207600109
Comments
©2012 National Academy of Sciences