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Mechanism of Thermal Reversal of the (Fulvalene)tetracarbonyldiruthenium Photoisomerization: Toward Molecular Solar–Thermal Energy Storage
Author(s) -
Kanai Yosuke,
Srinivasan Varadharajan,
Meier Steven K.,
Vollhardt K. Peter C.,
Grossman Jeffrey C.
Publication year - 2010
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201002994
Subject(s) - diradical , cyclopentadienyl complex , photoisomerization , mechanism (biology) , thermal , kinetics , chemistry , photochemistry , chemical physics , physics , thermodynamics , atomic physics , catalysis , organic chemistry , quantum mechanics , isomerization , singlet state , excited state
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 RuRu bond. The computed energy values agree well with all experimental data, including saturation kinetics for the trapping of the intermediate by CCl 4 . TS=transition state.