The C-C bond activation and recyclization of benzocyclobutenone to poly-fused rings catalyzed by the[Rh(R,S-L)]+complex producing the R,S-,S,R-,R,R-and S,S-product were investigated systematically at the BP86/6-31G(d,...The C-C bond activation and recyclization of benzocyclobutenone to poly-fused rings catalyzed by the[Rh(R,S-L)]+complex producing the R,S-,S,R-,R,R-and S,S-product were investigated systematically at the BP86/6-31G(d,p)level in gas phase and THF,and the R,S-and S,R-reaction pathways were revisited at the M062X/6-31G(d,p)level in THF.The computational results reveal that THF only marginally alters the free-energy barriers,but elevates the relative energies of all species.The BP86 functional testifies that in both gas phase and THF,the activation of strained C-C bonds bears relatively low free-energy barriers,and the rate-determining steps of S,R-and R,R-channels are different from those of R,S-and S,S-channels.The BP86 functional also predicts that the R,S-channel is energetically most favorable in gas phase,but the S,R-product is dominant in THF.The change of NPA charges can mirror the variation of molecular structures to elucidate reaction mechanisms.展开更多
基金supported by the National Natural Science Foundation of China(No.21571137)the Natural Science Foundation of Shandong Province(ZR2017LB010)the Science and Technology Planning Project(Guidance Plan)of Tai’an City(Nos.2018GX0041 and 2018GX0073)。
文摘The C-C bond activation and recyclization of benzocyclobutenone to poly-fused rings catalyzed by the[Rh(R,S-L)]+complex producing the R,S-,S,R-,R,R-and S,S-product were investigated systematically at the BP86/6-31G(d,p)level in gas phase and THF,and the R,S-and S,R-reaction pathways were revisited at the M062X/6-31G(d,p)level in THF.The computational results reveal that THF only marginally alters the free-energy barriers,but elevates the relative energies of all species.The BP86 functional testifies that in both gas phase and THF,the activation of strained C-C bonds bears relatively low free-energy barriers,and the rate-determining steps of S,R-and R,R-channels are different from those of R,S-and S,S-channels.The BP86 functional also predicts that the R,S-channel is energetically most favorable in gas phase,but the S,R-product is dominant in THF.The change of NPA charges can mirror the variation of molecular structures to elucidate reaction mechanisms.
