Photochemistry of (Fulvalene)tetracarbonyldiruthenium and Its Derivatives: Efficient Light Energy Storage Devices

摘要

Broad-band irradiation (λ_max=350 nm) of FvRu_2(CO)_4(1, Fv=η~5:η~5-bicyclopentadienyl) resuled in rapid isomerization to colorless (μ_2-η~1:η~-cyclopentadienyl)_2Ru_2(CO)_4 (2) in a novel process involving a formal dinuclear oxidative addition to a C-C bond. The product reverted to 1 upon heating in solution or in the solid state, under the latter conditions with an enthalpy change of -298.8 (1.5) kcal mol~_1. Mechanistic studies with a mixture of 1 and 1-d_8 revealed the absence of label scrambling, pointing to intramolecular pathways.