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Mechanism of Thermal Reversal of the (Fulvalene)tetracarbonyldiruthenium Photoisomerization: Toward Molecular Solar–Thermal Energy Storage

Authors

  • Dr. Yosuke Kanai,

    Corresponding author
    1. Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, Livermore, CA 94554 (USA)
    • Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, Livermore, CA 94554 (USA)
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  • Dr. Varadharajan Srinivasan,

    1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA)
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  • Dr. Steven K. Meier,

    1. Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460 (USA), Fax: (+1) 510-643-5208
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  • Prof. Dr. K. Peter C. Vollhardt,

    Corresponding author
    1. Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460 (USA), Fax: (+1) 510-643-5208
    • Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460 (USA), Fax: (+1) 510-643-5208
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  • Prof. Jeffrey C. Grossman

    Corresponding author
    1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA)
    • Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA)
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  • This study was supported by the Sustainable Products and Solutions Program at UC Berkeley and the NSF (CHE-0907800). Part of this work was performed under the auspices of the U.S. Department of Energy at Lawrence Livermore National Laboratory under Contract DE-AC52-07A27344. J.C.G. and V. S. are grateful for support for this work from the MIT Energy Initiative seed fund program. All calculations were performed at the National Energy Research Scientific Computing Center of the Lawrence Berkeley National Laboratory and at Lawrence Livermore National Laboratory. We thank Dusan Coso for performing the DSC experiments and Professors R. G. Bergman, A. Majumdar, and R. A. Segalman for valuable discussions.

Abstract

original image

A closer look at the title reaction pinpoints a surprising mechanism—a relatively rapid preequilibrium between cyclopentadienyl complex 2 and fulvalene diradical complex 1 precedes the rate-determining antisyn rotation and formation of the Ru[BOND]Ru bond. The computed energy values agree well with all experimental data, including saturation kinetics for the trapping of the intermediate by CCl4. TS=transition state.

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