Controlled introduction of functional groups at one P atom in [Cp*Fe(-P)] and release of functionalised phosphines.

By salt metathesis reactions of the anionic complexes of the type [CpFe(-PR)] (R = Bu (1a), Me (1b), -C[triple bond, length as m-dash]CPh (1c); Cp = 1,2,3,4,5-pentamethylcyclopentadienyl) with organic electrophiles (XR; X = halogen; R = (CH)Br, (CH)Br, Me) a variety of organo-substituted polyphosphorus ligand complexes of the type [CpFe(-PRR)] (2) are obtained. Thereby, organic substituents with different functional groups (FG), such as halogens or nitriles, are introduced. In [CpFe(-PRR')] (2a: R = Bu, R' = (CH)Br), the bromine substituent can be easily substituted, leading to functionalized complexes [{CpFe(-PBu)}(CH){CpFe(-PMe)}] (4) and [CpFe(-PRR')] (5) (R = Bu, R' = (CH)PPh) or by abstraction of a phosphine to the asymmetric substituted phosphine Bu(Bn)P(CH)Bn (6). The reaction of the dianionic species [K(dme)][CpFe(-P)] (I') with bromo-nitriles leads to [CpFe{-P((CH)CN)}] (7), allowing the introduction of two functional groups attached to one phosphorus atom. 7 reacts with ZnBr in a self-assembly reaction to form the supramolecular compound [CpFe{-P((CH)CN)}ZnBr] (8).