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
The systematic nucleophilic functionalisation of the cationic pentaphosphole ligand complex[Cp^(*)Fe(η^(4)-P_(5)Me)][OTf]([OTf]^(−)=[SO_(3)CF_(3)]^(−))(A)with sterically demanding Cp^(R)derivatives is reported.This n...The systematic nucleophilic functionalisation of the cationic pentaphosphole ligand complex[Cp^(*)Fe(η^(4)-P_(5)Me)][OTf]([OTf]^(−)=[SO_(3)CF_(3)]^(−))(A)with sterically demanding Cp^(R)derivatives is reported.This newly developed protocol turned out to be a highly reliable method for the synthesis of end-deck cyclo-P_(5)ligand complexes bearing bulky Cp^(R)substituents.By the reaction of A with anionic Cp^(R)salts,complexes of the type[Cp^(*)Fe(η^(4)-P_(5)MeCp^(R))](Cp^(*)=η^(5)-C_(5)Me_(5);Cp^(R)=Cp′(1),Cp″(2),Cp″′(3),Cp^(Me)(4);Cp′=η^(5)-C_(5)H_(4)^(t)Bu,Cp″=η^(5)-1,3-^(t)Bu_(2)C_(5)H_(3),Cp″′=η^(5)-1,3,4-^(t)Bu_(3)C_(5)H_(2),Cp^(Me)=η^(5)-C_(5)Me_(4)H)are obtained.All products feature a selective 1,1′-disubstitution at the cyclo-P_(5)ligand.Further reactivity studies of these complexes with FeBr_(2) enabled the formation of novel,sterically demanding ferrocene derivatives[{Cp^(*)Fe(η^(4)-P_(5)Me(η^(5)-Cp″))}_(2)Fe](5)and[Cp^(*)Fe(η^(4)-P_(5)Me(η^(5)-Cp″))FeCp″](6),featuring three different Fe atoms in a ferrocene-like environment.Oxidation of 5 yielded the dicationic complex[{Cp^(*)Fe(η^(4)-P_(5)Me(η^(5)-Cp″))}_(2)Fe][FAl]_(2)(7).EPR,zero-field ^(57)Fe Mössbauer,as well as DFT investigations on 7 showed a symmetric distribution of the positive charges on the outer Fe atoms.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The Deutsche Forschungsgemeinschaft(DFG)is gratefully acknowledged for the support within the project Sche 384/46-1 and Sche 384/38-3。
文摘The systematic nucleophilic functionalisation of the cationic pentaphosphole ligand complex[Cp^(*)Fe(η^(4)-P_(5)Me)][OTf]([OTf]^(−)=[SO_(3)CF_(3)]^(−))(A)with sterically demanding Cp^(R)derivatives is reported.This newly developed protocol turned out to be a highly reliable method for the synthesis of end-deck cyclo-P_(5)ligand complexes bearing bulky Cp^(R)substituents.By the reaction of A with anionic Cp^(R)salts,complexes of the type[Cp^(*)Fe(η^(4)-P_(5)MeCp^(R))](Cp^(*)=η^(5)-C_(5)Me_(5);Cp^(R)=Cp′(1),Cp″(2),Cp″′(3),Cp^(Me)(4);Cp′=η^(5)-C_(5)H_(4)^(t)Bu,Cp″=η^(5)-1,3-^(t)Bu_(2)C_(5)H_(3),Cp″′=η^(5)-1,3,4-^(t)Bu_(3)C_(5)H_(2),Cp^(Me)=η^(5)-C_(5)Me_(4)H)are obtained.All products feature a selective 1,1′-disubstitution at the cyclo-P_(5)ligand.Further reactivity studies of these complexes with FeBr_(2) enabled the formation of novel,sterically demanding ferrocene derivatives[{Cp^(*)Fe(η^(4)-P_(5)Me(η^(5)-Cp″))}_(2)Fe](5)and[Cp^(*)Fe(η^(4)-P_(5)Me(η^(5)-Cp″))FeCp″](6),featuring three different Fe atoms in a ferrocene-like environment.Oxidation of 5 yielded the dicationic complex[{Cp^(*)Fe(η^(4)-P_(5)Me(η^(5)-Cp″))}_(2)Fe][FAl]_(2)(7).EPR,zero-field ^(57)Fe Mössbauer,as well as DFT investigations on 7 showed a symmetric distribution of the positive charges on the outer Fe atoms.
