期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 109, 期 45, 页码 18295-18299出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1207600109
关键词
mass spectrometry; transient intermediates; C-H oxidation; catalysis
资金
- Air Force Office of Scientific Research [FA 9550-10-1-0235]
- National Science Foundation Center for Stereoselective C-H Functionalization (CSCHF)
- Center for Molecular Analysis and Design at Stanford University [1123893-1-AABGE]
- Department of Defense
- National Institutes of Health [5F32GM089033-02]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1205646] Funding Source: National Science Foundation
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.
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