The potential energy surface and reaction mechanism corresponding to the reaction of ytterbium monocation with fluoromethane, which represents a prototype of the activation of C-F bond in fluorohydrocarbons by bare la...The potential energy surface and reaction mechanism corresponding to the reaction of ytterbium monocation with fluoromethane, which represents a prototype of the activation of C-F bond in fluorohydrocarbons by bare lanthanide cations, have been investigated for the first time by using density functional theory. A direct fluorine abstraction mechanism was revealed, and the related thermochemistry data were determined. The electron-transfer reactivity of the reaction was analyzed using the two-state model, and a strongly avoided crossing behavior on the transition state region was shown. The present results support the reaction mechanism inferred from early experimental data and the related thermochemistry data can provide a guide for further experimental researches.展开更多
Here we describe the cation reduction and comproportionation as novel routes to synthesize electrolytes for rechargeable Mg-ion batteries.Reduction of the ammonium cation in[HNMe_(3)^(1+)][HCB_(11)H_(11)^(1-)]with met...Here we describe the cation reduction and comproportionation as novel routes to synthesize electrolytes for rechargeable Mg-ion batteries.Reduction of the ammonium cation in[HNMe_(3)^(1+)][HCB_(11)H_(11)^(1-)]with metallic Mg affords the halide free carborane salt[Mg^(2+)][HCB_(11)H_(11)^(1-)]2.Comproportionation of[Mg^(2+)][HCB_(11)H_(11)^(1-)]_(2) with MgPh_(2) affords the novel monocationic electrolyte[MgPh^(1+)][HCB_(11)H_(11)^(1-)],which reversibly deposits/strips Mg with a remarkable oxidative stability of 4.6 V vs.Mg^(0/+2).展开更多
基金supported by the National Science Foundation of Shandong Province(No.Z2000B02).
文摘The potential energy surface and reaction mechanism corresponding to the reaction of ytterbium monocation with fluoromethane, which represents a prototype of the activation of C-F bond in fluorohydrocarbons by bare lanthanide cations, have been investigated for the first time by using density functional theory. A direct fluorine abstraction mechanism was revealed, and the related thermochemistry data were determined. The electron-transfer reactivity of the reaction was analyzed using the two-state model, and a strongly avoided crossing behavior on the transition state region was shown. The present results support the reaction mechanism inferred from early experimental data and the related thermochemistry data can provide a guide for further experimental researches.
基金supported in part by the National Science Foundation(DMR-1508537).
文摘Here we describe the cation reduction and comproportionation as novel routes to synthesize electrolytes for rechargeable Mg-ion batteries.Reduction of the ammonium cation in[HNMe_(3)^(1+)][HCB_(11)H_(11)^(1-)]with metallic Mg affords the halide free carborane salt[Mg^(2+)][HCB_(11)H_(11)^(1-)]2.Comproportionation of[Mg^(2+)][HCB_(11)H_(11)^(1-)]_(2) with MgPh_(2) affords the novel monocationic electrolyte[MgPh^(1+)][HCB_(11)H_(11)^(1-)],which reversibly deposits/strips Mg with a remarkable oxidative stability of 4.6 V vs.Mg^(0/+2).
