The reaction of white phosphorus(P_(4))with phosphenium ions[R^(2)P]+yields[P5R^(2)]+cages via insertion of[R^(2)P]+into a P-P bond of P_(4).Herein,a systematic study on the reactivity of the P_(4) isolobal diphosphor...The reaction of white phosphorus(P_(4))with phosphenium ions[R^(2)P]+yields[P5R^(2)]+cages via insertion of[R^(2)P]+into a P-P bond of P_(4).Herein,a systematic study on the reactivity of the P_(4) isolobal diphosphorus complex[{CpMo(CO)_(2)}2(μ,η^(2:2)-P_(2))](A)towards differently substituted phosphenium ions was conducted.The phosphenium ions[R^(1)R^(2)P]+(R^(1)=R^(2)=Cl,Br and R^(1)=Ph,R^(2)=Cl)were found to insert into a Mo-P bond of A followed by an unprecedented halide shift to yield[{CpMo(CO)_(2)}_(2)(μ,η^(1:1:1:1)-P(R^(1))P(R^(2))P)][WCA](1a:R^(1)=R^(2)=Cl,[WCA]-=[BArF_(24)]^(-);1b:R^(1)=R^(2)=Br,[WCA]^(-)=[BArF_(24)]^(-);2:R^(1)=Ph,R^(2)=Cl,[WCA]^(-)=[TEF]^(-)with[BArF_(24)]^(-)=[B(3,5-C_(6)H_(3)(CF_(3))_(2))_(4)]^(-)and[TEF]^(-)=[Al{OC(CF_(3))_(3)}_(4)]^(-)).In contrast,[Ph_(2)P]^(+)reacts with A in a complex reaction involving Mo-P andMo-Mo bond insertion of the phosphenium ion leading to a mixture of[{CpMo(CO)}_(2)(μ_(4),η^(2:2:2:1:1)-2-(Ph_(2)P)P_(4))(μ-PPh_(2)){CpMo(CO)_(2)}_(2)][TEF]_(2)(3)and[{CpMo(CO)}_(2)(μ,η^(2:1:1)-PP(Cl)PPh_(2))(μ-PPh_(2))][TEF](4)depending on the used stoichiometry.Furthermore,the reaction of A with[Cy2P]+leads to CO elimination and formation of[{CpMo(CO)}2(μ,η^(2:2)-P_(2))(μ-PCy_(2))][TEF](5)in which the phosphenium ion bridges the Mo-Mo bond.Reaction monitoring and additional DFT computations shed light on the ongoing reaction pathways and reveal crucial intermediates of the respective reactions.展开更多
Using particle swarm optimization(PSO)methodology for crystal structure prediction,we predicted a novel two-dimensional(2 D)monolayer of silicide diphosphorus compound:SiP_(2),which exhibits good stability as examined...Using particle swarm optimization(PSO)methodology for crystal structure prediction,we predicted a novel two-dimensional(2 D)monolayer of silicide diphosphorus compound:SiP_(2),which exhibits good stability as examined via cohesive energy,mechanical criteria,molecular dynamics simulation and all positive phonon spectrum,respectively.The SiP_(2)monolayer is an indirect semiconductor with the band gap as 1.8484 eV(PBE)or 2.681 eV(HSE06),which makes it more advantageous for high-frequencyresponse optoelectronic materials.Moreover,the monolayer is a relatively hard auxetic material with negative Possion’s ratios,and also possesses a ultrahigh carrier mobility(1.069×10^(5)cm^(2)V^(-1)s^(-1))which is approximately four times the maximum value in phosphorene and comparable to the value of graphene and CP monolayers.Furthermore,the effects of strains on band structures and optical properties of SiP_(2)monolayer have been studied,as well as CO_(2)molecules can be strongly chemically adsorbed on the SiP_(2)monolayer.A semiconductor-to-metal transition for-9.5%strain ratio case and a huge optical absorption capacity on the order of 10^(6)cm^(-1)in visible region present.These theoretical findings endow SiP_(2)Monolayer to be a novel 2 D material holding great promises for applications in highperformance electronics,optoelectronics,mechanics and CO_(2)capturing material.展开更多
基金supported by the Deutsche Forschungsgemeinschaft(DFG)within the project Sche 384/36-2.R.S.is grateful for the Fonds der Chemischen Industrie for a PhD fellowship.C.R.is grateful to the Studienstiftung des Deutschen Volkes for a PhD fellowship.
文摘The reaction of white phosphorus(P_(4))with phosphenium ions[R^(2)P]+yields[P5R^(2)]+cages via insertion of[R^(2)P]+into a P-P bond of P_(4).Herein,a systematic study on the reactivity of the P_(4) isolobal diphosphorus complex[{CpMo(CO)_(2)}2(μ,η^(2:2)-P_(2))](A)towards differently substituted phosphenium ions was conducted.The phosphenium ions[R^(1)R^(2)P]+(R^(1)=R^(2)=Cl,Br and R^(1)=Ph,R^(2)=Cl)were found to insert into a Mo-P bond of A followed by an unprecedented halide shift to yield[{CpMo(CO)_(2)}_(2)(μ,η^(1:1:1:1)-P(R^(1))P(R^(2))P)][WCA](1a:R^(1)=R^(2)=Cl,[WCA]-=[BArF_(24)]^(-);1b:R^(1)=R^(2)=Br,[WCA]^(-)=[BArF_(24)]^(-);2:R^(1)=Ph,R^(2)=Cl,[WCA]^(-)=[TEF]^(-)with[BArF_(24)]^(-)=[B(3,5-C_(6)H_(3)(CF_(3))_(2))_(4)]^(-)and[TEF]^(-)=[Al{OC(CF_(3))_(3)}_(4)]^(-)).In contrast,[Ph_(2)P]^(+)reacts with A in a complex reaction involving Mo-P andMo-Mo bond insertion of the phosphenium ion leading to a mixture of[{CpMo(CO)}_(2)(μ_(4),η^(2:2:2:1:1)-2-(Ph_(2)P)P_(4))(μ-PPh_(2)){CpMo(CO)_(2)}_(2)][TEF]_(2)(3)and[{CpMo(CO)}_(2)(μ,η^(2:1:1)-PP(Cl)PPh_(2))(μ-PPh_(2))][TEF](4)depending on the used stoichiometry.Furthermore,the reaction of A with[Cy2P]+leads to CO elimination and formation of[{CpMo(CO)}2(μ,η^(2:2)-P_(2))(μ-PCy_(2))][TEF](5)in which the phosphenium ion bridges the Mo-Mo bond.Reaction monitoring and additional DFT computations shed light on the ongoing reaction pathways and reveal crucial intermediates of the respective reactions.
基金funded by the Scientific Research Fund of Hunan Provincial Education Department of China(No.16A081)the Natural Science Foundation of China(Nos.21603109,11304128)+2 种基金the Henan Joint Fund of the National Natural Science Foundation of China(No.U1404216)the Science and Technology Program of Henan Department of Science and Technology,China(No.182102310609)the Construct Program of Applied Characteristic Discipline in Hunan University of Science and Engineering(Mathematics,Electronic Science and Technology)。
文摘Using particle swarm optimization(PSO)methodology for crystal structure prediction,we predicted a novel two-dimensional(2 D)monolayer of silicide diphosphorus compound:SiP_(2),which exhibits good stability as examined via cohesive energy,mechanical criteria,molecular dynamics simulation and all positive phonon spectrum,respectively.The SiP_(2)monolayer is an indirect semiconductor with the band gap as 1.8484 eV(PBE)or 2.681 eV(HSE06),which makes it more advantageous for high-frequencyresponse optoelectronic materials.Moreover,the monolayer is a relatively hard auxetic material with negative Possion’s ratios,and also possesses a ultrahigh carrier mobility(1.069×10^(5)cm^(2)V^(-1)s^(-1))which is approximately four times the maximum value in phosphorene and comparable to the value of graphene and CP monolayers.Furthermore,the effects of strains on band structures and optical properties of SiP_(2)monolayer have been studied,as well as CO_(2)molecules can be strongly chemically adsorbed on the SiP_(2)monolayer.A semiconductor-to-metal transition for-9.5%strain ratio case and a huge optical absorption capacity on the order of 10^(6)cm^(-1)in visible region present.These theoretical findings endow SiP_(2)Monolayer to be a novel 2 D material holding great promises for applications in highperformance electronics,optoelectronics,mechanics and CO_(2)capturing material.
