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Comparison of the Reactivity of Nonheme Iron(IV)–Oxo versus Iron(IV)–Imido Complexes: Which is the Better Oxidant?

Authors

  • Anil Kumar Vardhaman,

    1. Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
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  • Prasenjit Barman,

    1. Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
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  • Suresh Kumar,

    1. Department of Applied Physics, Babasaheb Bhimrao Ambedkar University, School for Physical Sciences, Vidya Vihar, Rae Bareilly Road, Lucknow (UP), 226025 (India)
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  • Dr. Chivukula V. Sastri,

    Corresponding author
    1. Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)
    • Chivukula V. Sastri, Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)

      Devesh Kumar, Department of Applied Physics, Babasaheb Bhimrao Ambedkar University, School for Physical Sciences, Vidya Vihar, Rae Bareilly Road, Lucknow (UP), 226025 (India)

      Sam P. de Visser, Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester M1 7DN (United Kingdom)

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  • Dr. Devesh Kumar,

    Corresponding author
    1. Department of Applied Physics, Babasaheb Bhimrao Ambedkar University, School for Physical Sciences, Vidya Vihar, Rae Bareilly Road, Lucknow (UP), 226025 (India)
    • Chivukula V. Sastri, Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)

      Devesh Kumar, Department of Applied Physics, Babasaheb Bhimrao Ambedkar University, School for Physical Sciences, Vidya Vihar, Rae Bareilly Road, Lucknow (UP), 226025 (India)

      Sam P. de Visser, Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester M1 7DN (United Kingdom)

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  • Dr. Sam P. de Visser

    Corresponding author
    1. Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester M1 7DN (United Kingdom)
    • Chivukula V. Sastri, Department of Chemistry, Indian Institute of Technology Guwahati, Assam, 781039 (India)

      Devesh Kumar, Department of Applied Physics, Babasaheb Bhimrao Ambedkar University, School for Physical Sciences, Vidya Vihar, Rae Bareilly Road, Lucknow (UP), 226025 (India)

      Sam P. de Visser, Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science, The University of Manchester, 131 Princess Street, Manchester M1 7DN (United Kingdom)

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  • Research support was provided by the Department of Science and Technology, India (SR/S1/IC-02/2009) and Council for Scientific & Industrial Research (01(2527)/11/EMR-II) to C.V.S. The National Service of Computational Chemistry Software (NSCCS) is acknowledged for CPU time. D.K. acknowledges Department of Science and Technology (New Delhi) for a Ramanujan Fellowship.

Abstract

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Direkter Vergleich: Der erste detaillierte Reaktivitätsvergleich von Nicht-Häm-Eisen(IV)-Imido- und Nicht-Häm-Eisen(IV)-Oxo-Intermediaten mit Substraten ergab, dass die Eisen(IV)-Imido-Variante mit Sulfiden fünfmal schneller reagiert als ihr Eisen(IV)-Oxo-Pendant, während man bei der Wasserstoffatomabstraktion umgekehrte Verhältnisse beobachtet. Die Ergebnisse werden analysiert und erklärt.

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