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

Authors
Type
Published Article
Journal
Proceedings of the Latvian Academy of Sciences Section B Natural Exact and Applied Sciences
Publisher
De Gruyter Open Sp. z o.o.
Publication Date
Nov 14, 2012
Volume
109
Issue
45
Pages
18295–2147483647
Identifiers
DOI: 10.1073/pnas.1207600109
PMID: 23091019
PMCID: PMC3494934
Source
CCHF
License
Green

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.

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