The paper presented the results regarding the decomposition of gaseous CF_2ClB_r by cold plasma method.After two minutes discharge,the maximum decomposition rate of 2660 Pa CF_2ClB_r pure and 2660 Pa CF_2ClBr plus 798...The paper presented the results regarding the decomposition of gaseous CF_2ClB_r by cold plasma method.After two minutes discharge,the maximum decomposition rate of 2660 Pa CF_2ClB_r pure and 2660 Pa CF_2ClBr plus 7980 Pa O_2 reached 60% and 80%,respectively.The pa- per also studied the cold plasma gas phase chemistry reaction mechanism of CF_2ClBr at low pres- sure,and the pressure effects of CF_2ClBr and added gas(He,N_2,O_2 and dry air)on the CF_2ClBr decomposition respectively by cold plasma method.These studies will be helpful to application of cold plasma method in the treatment of hazardous gaseous wastes.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
文摘The paper presented the results regarding the decomposition of gaseous CF_2ClB_r by cold plasma method.After two minutes discharge,the maximum decomposition rate of 2660 Pa CF_2ClB_r pure and 2660 Pa CF_2ClBr plus 7980 Pa O_2 reached 60% and 80%,respectively.The pa- per also studied the cold plasma gas phase chemistry reaction mechanism of CF_2ClBr at low pres- sure,and the pressure effects of CF_2ClBr and added gas(He,N_2,O_2 and dry air)on the CF_2ClBr decomposition respectively by cold plasma method.These studies will be helpful to application of cold plasma method in the treatment of hazardous gaseous wastes.
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.
