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


Journal Article

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.

Full Text

Duke Authors

Cited Authors

  • Perry, RH; Cahill, TJ; Roizen, JL; Du Bois, J; Zare, RN

Published Date

  • November 2012

Published In

Volume / Issue

  • 109 / 45

Start / End Page

  • 18295 - 18299

PubMed ID

  • 23091019

Pubmed Central ID

  • 23091019

Electronic International Standard Serial Number (EISSN)

  • 1091-6490

International Standard Serial Number (ISSN)

  • 0027-8424

Digital Object Identifier (DOI)

  • 10.1073/pnas.1207600109


  • eng