Chemistry and Physics Faculty Articles

Document Type

Article

Publication Title

Proceedings of the National Academy of Sciences of the United States of America

ISSN

0027-8424

Publication Date

11-6-2012

Keywords

Mass spectrometry, Transient intermediates, C-H oxidation, Catalysis

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.

DOI

10.1073/pnas.1207600109

Volume

109

Issue

45

First Page

18295

Last Page

18299

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

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