Hexaphosphaferrocene [Fe(η5-P3C2tBu2)2] as a Connecting Moiety in Oligomeric and Polymeric Compounds

Abstract

The hexaphosphaferrocene complex [Fe(η5-P3C2tBu2)2] (1) derived from the corresponding 1,2,4-triphosphospholyl anion reacts with CuX (X = Cl, Br, I) in a 1 : 1 stoichiometry to give the isostructural, one-dimensional polymeric compounds [{Cu(μ3-X)}4{Fe(μ,η5:η1-P3C2tBu2)2}2]n (X = Cl (2), Br (3), I (4)), which display a unique sinusoidal (CuX)n ladder structure. In the reaction with CuI a second one-dimensional polymeric compound [{Cu3(μ-I)(μ3-I)2}(CH3CN){Fe(μ,η5:η1- P3C2tBu2)(μ3,η5:η1-P3C2tBu2)}]n (5) is formed. The reaction of 1 with CuX (X= Cl, Br, I) in a 1 : 2 stoichiometric ratio leads only in the case of CuCl to the formation of the new, oligomeric compound [{Cu(μ3-Cl)}4(CH3CN)2{Fe(μ,η5:η1-P3C2tBu2)2}2] (6), whereas in the case of CuBr and CuI the polymeric compounds 3 and 5 were isolated. The reaction of 1 with Ag[Al{OC(CF3)3}4] in a 1:1 stoichiometric ratio results in the formation of [Ag{Fe(μ,η5:η1-P3C2tBu2)2}2][Al{OC(CF3)3}4] (7), which shows dynamic behaviour in solution