Controlled introduction of functional groups at one P atom in [Cp*Fe(η⁵-P₅)] and release of functionalised phosphines

By salt metathesis reactions of the anionic complexes of the type [Cp*Fe(η⁴-P₅R)]^- (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^FG; X = halogen; R^FG = (CH₂)₃Br, (CH₂)₄Br, Me) a variety of organo-substituted polyphosphorus ligand complexes of the type [Cp*Fe(η⁴-P₅RR^FG)] (2) are obtained. Thereby, organic substituents with different functional groups (FG), such as halogens or nitriles, are introduced. In [Cp*Fe(η⁴-P₅RR')] (2a: R = Bu, R' = (CH₂)₃Br), the bromine substituent can be easily substituted, leading to functionalized complexes [{Cp*Fe(η⁴-P₅tBu)}(CH₂)₃{Cp*Fe(η⁴-P₅Me)}] (4) and [Cp*Fe(η⁴-P₅RR')] (5) (R = Bu, R' = (CH₂)₃PPh₂) or by abstraction of a phosphine to the asymmetric substituted phosphine tBu(Bn)P(CH₂)₃Bn (6). The reaction of the dianionic species [K(dme)₂]₂[Cp*Fe(η⁴-P₅)] (I') with bromo-nitriles leads to [Cp*Fe{η⁴-P₅((CH₂)₃CN)₂}] (7), allowing the introduction of two functional groups attached to one phosphorus atom. 7 reacts with ZnBr₂ in a self-assembly reaction to form the supramolecular compound [Cp*Fe{η⁴-P₅((CH₂)₃CN)₂}ZnBr₂] (8).