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.

Comments

©2012 National Academy of Sciences

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

DOI

10.1073/pnas.1207600109

Peer Reviewed

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