The first aliphatic phosphenium cation featuring a P-S bond (dimethylamino)(methylthio)phosphenium cation 1.has been prepared by treatument of the (dimethylamino)(methylthio) chlorophosphines 2 wih the stoichiometri q...The first aliphatic phosphenium cation featuring a P-S bond (dimethylamino)(methylthio)phosphenium cation 1.has been prepared by treatument of the (dimethylamino)(methylthio) chlorophosphines 2 wih the stoichiometri quantity of AlCl3 in CH2Cl2 solution, and charcterized by 1H 13C 27Al and 31P NMR spectroseopy展开更多
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
Ten years after the first synthesis of neutral two-coordinated phosphorus in 1962, the first phosphenium cations were synthesized by Fleming, Lupton and Jekot in 1972. Up to now, though 30 years have passed, the membe...Ten years after the first synthesis of neutral two-coordinated phosphorus in 1962, the first phosphenium cations were synthesized by Fleming, Lupton and Jekot in 1972. Up to now, though 30 years have passed, the members of these phosphenium cations are still very few. the research of phosphenium cations is only limited in France, America and other countries. In our laboratory work was done on a new unique cation: the 5-methylthio-3-N-phenyl-2,3-2(H)-1,3,4,2-thiadiazaphosphenium cation which was found and characterized by 261.9 ppm conclusively of ^(31)p NMR. It also has an electric conductivity in nucleophilic and electrophilic reactions. We are interested in noticing that these phospbenium cations are stabilized by one sulfur atom besides nitrogen atoms.展开更多
文摘The first aliphatic phosphenium cation featuring a P-S bond (dimethylamino)(methylthio)phosphenium cation 1.has been prepared by treatument of the (dimethylamino)(methylthio) chlorophosphines 2 wih the stoichiometri quantity of AlCl3 in CH2Cl2 solution, and charcterized by 1H 13C 27Al and 31P NMR spectroseopy
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Project supported by the National Natural Fund for Young Scientists
文摘Ten years after the first synthesis of neutral two-coordinated phosphorus in 1962, the first phosphenium cations were synthesized by Fleming, Lupton and Jekot in 1972. Up to now, though 30 years have passed, the members of these phosphenium cations are still very few. the research of phosphenium cations is only limited in France, America and other countries. In our laboratory work was done on a new unique cation: the 5-methylthio-3-N-phenyl-2,3-2(H)-1,3,4,2-thiadiazaphosphenium cation which was found and characterized by 261.9 ppm conclusively of ^(31)p NMR. It also has an electric conductivity in nucleophilic and electrophilic reactions. We are interested in noticing that these phospbenium cations are stabilized by one sulfur atom besides nitrogen atoms.
