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Phenylthiolate-diironhexacarbonyl complexes: a comparative conceptual DFT and electrochemical study

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Abstract

The electrocatalytic reduction of acetic acid by the previously studied [(μ-biphenyl-2,2′-dithiolato)2Fe2(CO)6] (1), has been explored. Complex 1 generates hydrogen at −2.53 V versus Fc/Fc+. Comparatively, the overpotential for the reduction of protons to hydrogen by 1 (1.07 V vs Fc/Fc+) is higher by 270 mV than that of the non-bridging analog [(μ-SPh)2Fe2(CO)6] (2). Global reactivity descriptors, chemical hardness and electrophilicity index for 1 and 2 have been computed from frontier molecular orbital energies determined using HF and DFT/B3LYP methods. The results indicate that complex 1 is softer with a higher electrophilicity index than 2, in agreement with the minimum electrophilicity principle.

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Acknowledgments

The authors gratefully acknowledge support for this work from ATU undergraduate research grant and the Computational Facilities at Coastal Carolina University.

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Authors and Affiliations

  1. Department of Physical Sciences, College of Natural and Health Sciences, Arkansas Tech University, 1701 N. Boulder Ave., Russellville, AR, 72801, USA

    Jazlynn C. Wisener, Kaitlin T. Patton & Charles A. Mebi

  2. Department of Chemistry and Physics, Coastal Carolina University, P.O. Box 261954, Conway, SC, 29528-6054, USA

    Johnson K. Agbo

Authors
  1. Jazlynn C. Wisener
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  2. Kaitlin T. Patton
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  3. Johnson K. Agbo
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  4. Charles A. Mebi
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Correspondence to Johnson K. Agbo or Charles A. Mebi.

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Wisener, J.C., Patton, K.T., Agbo, J.K. et al. Phenylthiolate-diironhexacarbonyl complexes: a comparative conceptual DFT and electrochemical study. Transition Met Chem 41, 339–345 (2016). https://doi.org/10.1007/s11243-016-0028-5

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  • DOI: https://doi.org/10.1007/s11243-016-0028-5

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