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Experiment and Theory Reveal the Fundamental Difference between Two-State and Single-State Reactivity Patterns in Nonheme FeIV[DOUBLE BOND]O versus RuIV[DOUBLE BOND]O Oxidants

Authors

  • Sunder N. Dhuri Dr.,

    1. Department of Chemistry, Division of Nano Sciences, and Centre for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea, Fax: (+82) 2-3277-4441
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  • Mi Sook Seo Dr.,

    1. Department of Chemistry, Division of Nano Sciences, and Centre for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea, Fax: (+82) 2-3277-4441
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  • Yong-Min Lee Dr.,

    1. Department of Chemistry, Division of Nano Sciences, and Centre for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea, Fax: (+82) 2-3277-4441
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  • Hajime Hirao Dr.,

    1. Department of Organic Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel, Fax: (+972) 2-658-4680
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  • Yong Wang Dr.,

    1. Department of Organic Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel, Fax: (+972) 2-658-4680
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  • Wonwoo Nam Prof. Dr.,

    1. Department of Chemistry, Division of Nano Sciences, and Centre for Biomimetic Systems, Ewha Womans University, Seoul 120-750, Korea, Fax: (+82) 2-3277-4441
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  • Sason Shaik Prof. Dr.

    1. Department of Organic Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem, 91904 Jerusalem, Israel, Fax: (+972) 2-658-4680
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  • The research at EWU was supported by KOSEF/MOST through CRI Program and the research at HU was supported by the Ministry of Education and Research within the Framework of the German-Israeli Project Cooperation (DIP). H.H. was supported by the JSPS Postdoctoral Fellowship for Research Abroad.

Abstract

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Zwei reaktive Zustände, ein Triplett-Grundzustand und ein nur wenig höher liegender angeregter Quintettzustand, führen – je nach den elektronischen Verhältnissen des axialen Liganden X – zu entgegengesetzten Reaktivitäten von FeIV-Oxokomplexen in O-Transfer- und H-Abstraktionsreaktionen (siehe Bild). Bei den RuIV-Analoga werden beide Reaktivitäten dagegen einzig durch die Elektrophilie des Komplexes bestimmt, da der Quintettzustand nicht verfügbar ist.

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