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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.