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
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.
