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New types of triple-decker complexes with an organo-substituted P 5 middle-deck were synthesized by the reaction of [Cp*Fe(η 4 -P 5 R)] - (1a: R = CH 2 SiMe 3 ; 1b: R = NMe 2 ) 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,η 4:3 -P 5 CH 2 SiMe 3 )] 2a with [Cp 2 Fe][PF 6 ], the cationic complex [(Cp*Fe)(Cp'''Co)(μ,η 5:4 -P 5 CH 2 SiMe 3 )] + was isolated. The electronic structure of the synthesized complexes was elucidated by DFT calculations.

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

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