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Activation of C(sp2)-X and C(sp3)-X σ-Bonds (X = F, Cl, Br, and OMe) by Rhodium Complex with Pincer-Type Aluminyl
Yangyang Hu1,2, Shigeyoshi Sakaki1
1Institute for Integrated Cell-Material Sciences, Kyoto University, Kyoto-daigaku Katsura, Nishikyo-ku, Kyoto 615-8246, Japan.
Abstract:
C(sp2)-X (X = F, Cl, Br, and OMe) σ-bond activation of halo- and methoxybenzenes and C(sp3)-X (X = F and Cl) σ-bond activation of fluoro- and chloromethanes by a rhodium complex with pincer-type aluminyl ligand (named Rh(PAlP)) are theoretically studied. Rh(PAlP) exhibits high reactivity in difficult σ-bond activations and flexible dependence of reaction mechanism on substrate and solvent. In the gas phase and cyclohexane solvent, all the C(sp2)-X σ-bond activations occur via cooperative activation by the Rh-Al moiety (Pathway 1) with moderate Gibbs activation energy (ΔG°‡). In polar THF solvent, C(sp2)-Cl and C(sp2)-Br σ-bond activations occur via nucleophilic attack of Rh to the phenyl group (Pathway 3) with a moderate ΔG°‡ value, whereas even in THF solvent, C(sp2)-F and C(sp2)-OMe σ-bond activations occur via Pathway 1. Concerted oxidative addition to the Rh atom (Pathway 2) is not preferred in these substrates. C(sp3)-F σ-bond activation of fluoromethane occurs via Pathway 1 in the THF solvent, while C(sp3)-Cl σ-bond activation occurs via Pathway 2. The transition state of Pathway 3 could not be optimized in the halomethane case. The reactivity of Rh(PAlP) and flexible dependence of the reaction mechanism on the substrate and solvent result from the presence of a Rh-Al direct bond, Alδ+···Xδ- attractive interaction, and the strongly donating nature of the aluminyl ligand.
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