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| 概要 |
Thermal or photochemical isomerization of dinuclear carbonyl species bound to conjugate π-systems is presented Typically, irradiation of a diiron carbonyl complex, (μ_2:η^3:η^5-acenaphthylene)Fe_2(CO)..._5 (3), induced the haptotropic rearrangement to give the isomer 4. The product reverted to 3 by protecting its solution from the light with an enthalpy change of 2 kcal/mol. The activation energies estimated from the kinetic data of the revert process (4 to 3) were ΔH^‡_<298>=21kcal/mol, and ΔS^‡_<298>=-6cal/mol・deg. Similar haptotropic rearrangement was observed in thermal and photochemical reactions between two haptotropic isomers of (μ_2:η^3:η^5-guaiazulene)Fe_2(CO)_5, 7 and 8. Interconversion between 7 and 8 occurred both thermally and photochemically; the thermal equilibrium ratio between 7 and 8 was 55:45, whereas the isomer ratio at the photostatic state was 35:65. The results showed that dinuclear metal carbonyls, in particular the compound 3, can capture energy by undergoing a transformation to a metastable species.続きを見る
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Mendeley出力
KJ00004507851