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The Origins of Dramatic Axial Ligand Effects: Closed-Shell MnVO Complexes Use Exchange-Enhanced Open-Shell States to Mediate Efficient H Abstraction Reactions

Authors

  • Dr. Deepa Janardanan,

    1. Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)
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  • Dr. Dandamudi Usharani,

    1. Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)
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  • Prof. Dr. Sason Shaik

    Corresponding author
    1. Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)
    • Institute of Chemistry and The Lise Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University, Jerusalem, 91904 (Israel)
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  • Support by Minerva is thanked. Prof. H. Schwarz is thanked for pointing out the closed–open issue and reading the paper.

Abstract

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Spin-state effects: In [(Cz)MnVO] complexes, even with singlet closed-shell ground states, the reactive state is the open-shell triplet B state (SB=1) that has a high oxyl radical character and a transition state (TS) stabilized by exchange-enhanced reactivity (EER; see picture). The dramatic axial ligand effect originates in the EER of this state.

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