Capturing fleeting intermediates in a catalytic C-H amination reaction cycle

Richard H. Perry, Thomas J. Cahill, Jennifer L. Roizen, Justin Du Bois, Richard N. Zare

Research output: Contribution to journalArticle

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.

Original languageEnglish (US)
Pages (from-to)18295-18299
Number of pages5
JournalProceedings of the National Academy of Sciences of the United States of America
Volume109
Issue number45
DOIs
StatePublished - Nov 6 2012

Keywords

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

ASJC Scopus subject areas

  • General

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