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Resonance Raman spectroscopy as an in situ probe for monitoring catalytic events in a Ru–porphyrin mediated amination reaction

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journal contribution
posted on 03.08.2016, 14:17 by Paolo Zardi, Emma Gallo, Gregory A. Solan, Andrew J. Hudson
Resonance Raman microspectroscopy has been widely used to study the structure and dynamics of porphyrins and metal complexes containing the porphyrin ligand. Here, we have demonstrated that the same technique can be adapted to examine the mechanism of a homogeneously-catalysed reaction mediated by a transition-metal-porphyrin complex. Previously it has been challenging to study this type of reaction using in situ spectroscopic monitoring due to the low stability of the reaction intermediates and elevated-temperature conditions. We have made a straightforward modification to the sample stage on a microscope for time-lapsed Raman microspectroscopy from reaction mixtures in these media. The allylic amination of unsaturated hydrocarbons by aryl azides, which can be catalysed by a ruthenium-porphyrin complex, has been used as an illustrative example of the methodology. The mechanism of this particular reaction has been studied previously using density-functional theory and kinetic approaches. The Raman measurements support the mechanism proposed in the earlier publications by providing the first experimental verification of a precursor reaction complex between the aryl azide and the ruthenium metal ion, and evidence for the formation of a mono-imido intermediate complex under conditions of high concentration of the reactant olefin.

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Citation

Analyst, 2016, 141 (10), pp. 3050-3058

Author affiliation

/Organisation/COLLEGE OF SCIENCE AND ENGINEERING/Department of Chemistry

Version

AM (Accepted Manuscript)

Published in

Analyst

Publisher

Royal Society of Chemistry

issn

0003-2654

eissn

1364-5528

Acceptance date

30/03/2016

Copyright date

2016

Available date

30/03/2017

Publisher version

http://pubs.rsc.org/en/Content/ArticleLanding/2016/AN/C6AN00333H#!divAbstract

Notes

Corrected by http://hdl.handle.net/2381/39231 DOI 10.1039/C6AN90078J

Language

en

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