Controlled introduction of functional groups at one P atom in [Cp*Fe( η 5 -P 5 )] and release of functionalised phosphines.

By salt metathesis reactions of the anionic complexes of the type [Cp*Fe( η 4 -P 5 R)] - (R = t 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 = (CH 2 ) 3 Br, (CH 2 ) 4 Br, Me) a variety of organo-substituted polyphosphorus ligand complexes of the type [Cp*Fe( η 4 -P 5 RR FG )] (2) are obtained. Thereby, organic substituents with different functional groups (FG), such as halogens or nitriles, are introduced. In [Cp*Fe( η 4 -P 5 RR')] (2a: R = t Bu, R' = (CH 2 ) 3 Br), the bromine substituent can be easily substituted, leading to functionalized complexes [{Cp*Fe( η 4 -P 5 t Bu)}(CH 2 ) 3 {Cp*Fe( η 4 -P 5 Me)}] (4) and [Cp*Fe( η 4 -P 5 RR')] (5) (R = t Bu, R' = (CH 2 ) 3 PPh 2 ) or by abstraction of a phosphine to the asymmetric substituted phosphine t Bu(Bn)P(CH 2 ) 3 Bn (6). The reaction of the dianionic species [K(dme) 2 ] 2 [Cp*Fe( η 4 -P 5 )] (I') with bromo-nitriles leads to [Cp*Fe{ η 4 -P 5 ((CH 2 ) 3 CN) 2 }] (7), allowing the introduction of two functional groups attached to one phosphorus atom. 7 reacts with ZnBr 2 in a self-assembly reaction to form the supramolecular compound [Cp*Fe{ η 4 -P 5 ((CH 2 ) 3 CN) 2 }ZnBr 2 ] n (8).