| Autor: |
Shimogawa, Ryuichi, Muroi, Yuki, Noguchi, Naoya, Konishi, Gen-ichi, Takao, Toshiro, Suzuki, Hiroharu |
| Zdroj: |
Organometallics; December 2022, Vol. 41 Issue: 23 p3750-3761, 12p |
| Abstrakt: |
In contrast to the thermal reaction of [Cp*Ru(μ-H)4RuCp*] (1: Cp* = η5-C5Me5) with benzene at 70 °C yielding an equilibrium mixture of 1and [{Cp*Ru(μ-H)}2(μ-η2:η2-C6H8)] (2), the UV irradiation of 1at 25 °C in benzene at 365 nm exclusively produced the dinuclear cyclohexadiene complex 2. The photo-induced reaction of 1featured remarkably high tolerance toward substituted benzene, including toluene and p-xylene. The photo-induced reaction of 1with toluene afforded a regio-isomeric mixture of bridging methylcyclohexadiene complexes 5aand 5bin high yields, although the thermal reaction of 1with toluene did not proceed. Dearomatization via insertion into the Ru–H bond did not occur in the reaction with the fused aromatic system due to the preservation of the additional aromatic system. The η2:η2-5,6-benzocyclohexadiene complex, [{Cp*Ru(μ-H)}2(μ-η2:η2-C10H8)] (7), was selectively obtained in the photo-induced reaction of 1with naphthalene. Photochemically induced transient species with an expanded Ru2skeleton were proposed based on the thermal reaction of 2,6-dimethylcyclohexa-1,3-diene complex, [{Cp*Ru(μ-H)}2(μ-η2:η2-Me2C6H6)] (6), with toluene, yielding the mixture of 5aand 5b. Time-dependent density functional theory calculations of 1provided insight into the mechanism. |
| Databáze: |
Supplemental Index |
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