Triple-decker sandwich complexes with a bent cyclo-P5 middle-deck.

New types of triple-decker complexes with an organo-substituted P5 middle-deck were synthesized by the reaction of [Cp*Fe(η4-P5R)]- (1a: R = CH2SiMe3; 1b: R = NMe2) with halogeno-bridged transition metal dimers [Cp'''MX]2 (M = Cr, Fe, Co, Ni; X = Cl, Br). By oxidation of [(Cp*Fe)(Cp'''Co)(μ,η4:3-P5CH2SiMe3)] 2a with [Cp2Fe][PF6], the cationic complex [(Cp*Fe)(Cp'''Co)(μ,η5:4-P5CH2SiMe3)]+ was isolated. The electronic structure of the synthesized complexes was elucidated by DFT calculations.