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Dr. Yosuke Kanai, Dr. Varadharajan Srinivasan, Dr. Steven K. Meier, Prof. Dr. K. Peter C. Vollhardt and Prof. Jeffrey C. Grossman Mechanism of Thermal Reversal of the (Fulvalene)tetracarbonyldiruthenium Photoisomerization: Toward Molecular Solar–Thermal Energy Storage Angewandte Chemie International Edition 49

Version of Record online: 14 OCT 2010 | DOI: 10.1002/anie.201002994

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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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