Communication

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

  1. Dr. Yosuke Kanai3,*,
  2. Dr. Varadharajan Srinivasan2,
  3. Dr. Steven K. Meier1,
  4. Prof. Dr. K. Peter C. Vollhardt1,* and
  5. Prof. Jeffrey C. Grossman2,*

Article first published online: 14 OCT 2010

DOI: 10.1002/anie.201002994

Issue

Angewandte Chemie International Edition

Angewandte Chemie International Edition

Volume 49, Issue 47, pages 8926–8929, November 15, 2010


Additional Information

How to Cite

Kanai, Y., Srinivasan, V., Meier, S. K., Vollhardt, K. P. C. and Grossman, J. C. (2010), Mechanism of Thermal Reversal of the (Fulvalene)tetracarbonyldiruthenium Photoisomerization: Toward Molecular Solar–Thermal Energy Storage. Angew. Chem. Int. Ed., 49: 8926–8929. doi: 10.1002/anie.201002994

Author Information

  1. 1

    Department of Chemistry, University of California at Berkeley, Berkeley, CA 94720-1460 (USA), Fax: (+1) 510-643-5208

  2. 2

    Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA)

  3. 3

    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)

  1. †

    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.

Publication History

  1. Issue published online: 11 NOV 2010
  2. Article first published online: 14 OCT 2010
  3. Manuscript Received: 17 MAY 2010

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Keywords:

  • ab initio calculations;
  • C[BOND]C activation;
  • isomerization;
  • photochemistry;
  • ruthenium
Thumbnail image of graphical abstract

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 anti–syn 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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