The reaction between tripodal trisamidophosphine ligand H_(3)PN_(3)^(Ar)and V(Mes)_(3)(THF)(Mes=mesityl)yields the vanadium(Ⅲ)complex(PN_(3)^(Ar))V(1)with an open site in the axial position,which could coordinate wit...The reaction between tripodal trisamidophosphine ligand H_(3)PN_(3)^(Ar)and V(Mes)_(3)(THF)(Mes=mesityl)yields the vanadium(Ⅲ)complex(PN_(3)^(Ar))V(1)with an open site in the axial position,which could coordinate with THF,pyridine,and NH_(3)to form the corresponding adducts(2—4).The vanadium(Ⅲ)center is redox-active,as demonstrated by cyclic voltammetry methods and chemical oxidation or reduction.Notably,a novel dinitrogen divanadium complex with a bridging N_(2)ligand,{K(THF)}_(2){[PN_(3)^(Ar)]V}_(2)(μ-N_(2))(6),was synthesized via treatment of 1 with 1 equivalent of potassium naphthalenide in THF under a N_(2)atmosphere.The electronic structures and binding properties of 6 are evaluated and discussed based on its DFT calculations.Additionally,these vanadium complexes(1,5,6)can serve as catalysts for the conversion of N_(2)into N(SiMe_(3))_(3) in the presence of reductants and Me_(3)SiCl.展开更多
基金supported by the National Natural Science Foundation of China(21988101 for Z.-J.S.,22201044 for D.-D.Z.,22071029 for F.L.)Fundamental Research Funds for the Central Universities(20720220010).
文摘The reaction between tripodal trisamidophosphine ligand H_(3)PN_(3)^(Ar)and V(Mes)_(3)(THF)(Mes=mesityl)yields the vanadium(Ⅲ)complex(PN_(3)^(Ar))V(1)with an open site in the axial position,which could coordinate with THF,pyridine,and NH_(3)to form the corresponding adducts(2—4).The vanadium(Ⅲ)center is redox-active,as demonstrated by cyclic voltammetry methods and chemical oxidation or reduction.Notably,a novel dinitrogen divanadium complex with a bridging N_(2)ligand,{K(THF)}_(2){[PN_(3)^(Ar)]V}_(2)(μ-N_(2))(6),was synthesized via treatment of 1 with 1 equivalent of potassium naphthalenide in THF under a N_(2)atmosphere.The electronic structures and binding properties of 6 are evaluated and discussed based on its DFT calculations.Additionally,these vanadium complexes(1,5,6)can serve as catalysts for the conversion of N_(2)into N(SiMe_(3))_(3) in the presence of reductants and Me_(3)SiCl.
