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(eta(4)-P5R)](-) (R = Bu-t (1a), Me (1b), -C equivalent to CPh (1c); Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) with organic electrophiles (XRFG; X = halogen; R-FG = (CH2)(3)Br, (CH2)(4)Br, Me) a variety of organo-substituted polyphosphorus ligand complexes of the type [Cp*Fe(eta(4)-P5RRFG)] (2) are obtained. Thereby, organic substituents with different functional groups (FG), such as halogens or nitriles, are introduced. In [Cp*Fe(eta(4)-P5RR')] (2a: R = Bu-t, R' = (CH2)(3)Br), the bromine substituent can be easily substituted, leading to functionalized complexes [{Cp*Fe(eta(4)-P(5)tBu)} (CH2)(3){Cp*Fe(eta(4)-P5Me)}] (4) and [Cp * Fe(eta(4)-P5RR')] (5) (R = tBu, R' = (CH2)(3)PPh2) or by abstraction of a phosphine to the asymmetric substituted phosphine tBu(Bn)P(CH2)(3)Bn (6). The reaction of the dianionic species [K(dme)(2)](2)[Cp*Fe(eta(4)-P-5)] (I') with bromo-nitriles leads to [Cp*Fe{eta(4)-P-5((CH2)(3)CN)(2)}] (7), allowing the introduction of two functional groups attached to one phosphorus atom. 7 reacts with ZnBr2 in a selfassembly reaction to form the supramolecular compound [Cp*Fe{eta(4)-P-5((CH2)(3)CN)(2)}ZnBr2](n) (8).

Automated summary

By performing salt metathesis reactions, a variety of organo-substituted polyphosphorus ligand complexes [Cp*Fe(eta(4)-P5RRFG)] (2) can be obtained through the reaction of anionic complexes [Cp*Fe(eta(4)-P5R)](-) with organic electrophiles. Different functional groups can be introduced through this reaction. The reaction of dianionic species [K(dme)(2)](2)[Cp*Fe(eta(4)-P-5)] with bromo-nitriles allows the introduction of two functional groups attached to one phosphorus atom, and the self-assembly reaction between the resulting compound and ZnBr2 forms a supramolecular compound.