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Paramagnetic Resonance of High-Spin Co(II) in Biologically-Relevant Environments: Models to Metalloproteins

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Future Directions in Metalloprotein and Metalloenzyme Research

Part of the book series: Biological Magnetic Resonance ((BIMR,volume 33))

Abstract

The use of Co(II) as a spectroscopic surrogate for Zn(II) is now a well-established protocol in metallobiochemistry. The d 7 Co(II) ion usually adopts a high-spin (S = 3/2) configuration and a coordination geometry similar to the native Zn(II) ion, often returning an active enzyme. However, the complicated electronic structure that gives rise to easily detectable signals in a wide array of optical and magnetic spectroscopies simultaneously hampers data interpretation in terms of structure. Nowhere is this more evident than in the EPR spectra of Co(II) complexes, particularly at X-band. Some alternatives to common practice in the assignment and simulation of high-spin Co(II) EPR are presented. Our intent is to shed light on the sources of spectral complexity, and address some of the remaining issues confounding the successful application of more advanced techniques, such as ENDOR (CW or pulsed) and ESEEM. The importance of spin sub-level mixing into the magnetic ground state, leading to possible intensity stealing and the appearance of signals from both spin doublets, is discussed in terms of available zero-field splitting data, and the identity of the ground doublet.

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Acknowledgements

This work was supported by the US National Science Foundation (CHE-0518189, CHE-0964806, CHE-0909985 and CHE-1152755 to D.L.T.).

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Miami University, Oxford, OH, 45056, USA

    Robert R. Baum, Christopher D. James & David L. Tierney

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  1. Robert R. Baum
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  2. Christopher D. James
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  3. David L. Tierney
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Correspondence to David L. Tierney .

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  1. Brisbane, Australia

    Graeme Hanson

  2. Department of Chemistry and Biochemistry, University of Denver, Denver, Colorado, USA

    Lawrence Berliner

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Baum, R.R., James, C.D., Tierney, D.L. (2017). Paramagnetic Resonance of High-Spin Co(II) in Biologically-Relevant Environments: Models to Metalloproteins. In: Hanson, G., Berliner, L. (eds) Future Directions in Metalloprotein and Metalloenzyme Research. Biological Magnetic Resonance, vol 33. Springer, Cham. https://doi.org/10.1007/978-3-319-59100-1_3

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