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

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 rea...

Full description

Saved in:
Bibliographic Details
Published in:Proceedings of the National Academy of Sciences - PNAS 2012-11, Vol.109 (45), p.18295-18299
Main Authors: Perry, Richard H, Cahill, Thomas J, Roizen, Jennifer L, Du Bois, Justin, Zare, Richard N
Format: Article
Language:English
Subjects:
Adducts
Amination
Analytical chemistry
analytical methods
Atoms
Atoms & subatomic particles
Catalysis
Chemical reactions
Desorption
Hydrocarbons
hydrogen
Ionization
Isotopes
Mass spectra
Mass spectrometry
Mass spectroscopy
oxidants
Oxidation
Physical Sciences
Sulfonamides
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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.
ISSN:0027-8424
1091-6490
DOI:10.1073/pnas.1207600109