the reaction of C_(60) with methyl bromacetate in the presence of Sml_2 gives the title compound 1-methoxycarbonylmethy1-21hydrofullerene in good yield.
Efforts to develop organometallic complexes for catalytic nitrogen reduction have seen significant progress in recent years.However,the strategies for improving the activity of the homogenous catalysts have mainly foc...Efforts to develop organometallic complexes for catalytic nitrogen reduction have seen significant progress in recent years.However,the strategies for improving the activity of the homogenous catalysts have mainly focused on alternating ligands and metals.Herein,we report that the activity and stability of a PN_(P-Mo pincer complex(2)toward dinitrogen(N_(2))reduction were greatly enhanced through postmodification of the PN^(3)P pincer framework of its parent complex(1).A high ratio of NH_(3)/Mo(3525)was achieved in the presence of SmI_(2)as a reductant.In sharp contrast,1 only afforded an NH_(3)/Mo ratio of 21.Moreover,when supported by an anionic pincer ligand,2 furnished a high oxidation state Mo(V)-nitride complex via N_(2)cleavage as a plausible key intermediate in the catalytic process,suggesting a catalytic cycle that may involve different oxidation states(Ⅱ/Ⅴ)from those with 10-πelectron configuration in the literature.展开更多
基金National Natural Science Foundation of China!No.29825102
文摘the reaction of C_(60) with methyl bromacetate in the presence of Sml_2 gives the title compound 1-methoxycarbonylmethy1-21hydrofullerene in good yield.
文摘Efforts to develop organometallic complexes for catalytic nitrogen reduction have seen significant progress in recent years.However,the strategies for improving the activity of the homogenous catalysts have mainly focused on alternating ligands and metals.Herein,we report that the activity and stability of a PN_(P-Mo pincer complex(2)toward dinitrogen(N_(2))reduction were greatly enhanced through postmodification of the PN^(3)P pincer framework of its parent complex(1).A high ratio of NH_(3)/Mo(3525)was achieved in the presence of SmI_(2)as a reductant.In sharp contrast,1 only afforded an NH_(3)/Mo ratio of 21.Moreover,when supported by an anionic pincer ligand,2 furnished a high oxidation state Mo(V)-nitride complex via N_(2)cleavage as a plausible key intermediate in the catalytic process,suggesting a catalytic cycle that may involve different oxidation states(Ⅱ/Ⅴ)from those with 10-πelectron configuration in the literature.
