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.
