Topics in Catalysis

, Volume 58, Issue 12–13, pp 759–768 | Cite as

The Role of Low Valent Transition Metal Complexes in Homogeneous Catalysis: An EPR Investigation

Original Paper
First Online:

Abstract

Electron paramagnetic resonance (EPR) spectroscopy is an extremely versatile technique for the characterisation of homogeneous catalysts involving paramagnetic centres. The paramagnetic parent pre-catalyst, the activated catalyst itself or any resulting reactive intermediates, can all be monitored in situ in order to delineate the role of the formal metal oxidation state and the influence of ligand structure on the resulting catalytic activity. In this review of our recent results, we describe how highly reactive, low valent transition metal complexes of formal oxidation states Ni(I), Fe(I) and Cr(I) coordinated by N-heterocyclic carbene (NHC) or phosphine ligands and which are active for a range of cross-coupling reactions or ethylene oligomerisation, have been investigated by EPR. Analysis of the EPR spectra revealed (i) how the influence of the NHC ring size affects the electronic properties of the Ni(I) centre, (ii) how low spin Fe(I) intermediates are catalytically competent on-cycle species in cross-coupling reactions and (iii) how intramolecular structural rearrangements involving Cr(I) centres occur following the addition of a co-catalyst to the reaction medium. These results demonstrate the utility of EPR to probe the structure–reactivity relationships in paramagnetic homogeneous catalysts, providing information not readily accessible by other techniques.

Keywords

EPR spectroscopy Low-valent Homogeneous catalysis Cross-coupling Oligomerisation Transition metals 
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Notes

Acknowledgments

We would like to express our gratitude to our colleagues, Prof. Robin Bedford (Bristol University, UK) and Prof. Michael Whittlesey (University of Bath, UK), for fruitful discussions. We also acknowledge financial support from EPSRC (EP/K017322).

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Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  1. 1.School of ChemistryCardiff UniversityCardiffUK

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