Coordination chemistry of [Cp*Fe(η5-P3C2tBu2)] (Cp*=η5-C5Me5) with copper(I) halides – Formation of oligomeric and polymeric compounds

The reaction of the 1,2,4-triphosphaferrocene [Cp*Fe(η5-P3C2tBu2)] (1) with CuX (X = Cl, Br, I) in a 1:1 stoichiometric ratio leads to the formation of the oligomeric compounds [{Cu(μ-X)}6(μ6-X)Cu(MeCN)3{μ,η2-(Cp*Fe(η5-P3C2tBu2))}2{μ3,η3-(Cp*Fe(η5-P3C2tBu2))}] (X = Cl (2), Br (3)) and [{Cu(μ-I)}3{Cu(μ3-I)}3Cu(μ6-I){μ,η2-(Cp*Fe(η5-P3C2tBu2))}3{η1-(Cp*Fe(η5-P3C2tBu2))}] (4) revealing Cu(I) halide cages surrounded by 1,2,4-triphosphaferrocene moieties. The reaction of [Cp*Fe(η5-P3C2tBu2)] with CuI in a 1:4 stoichiometry leads to the formation of the two-dimensional polymer [{Cu(μ-I)}4{Cu(μ3-I)(MeCN)}2{μ3,η3-(Cp*Fe(P3C2tBu2))}]n (5). The oligomeric compounds show dynamic behavior in solution monitored by 31P NMR spectroscopy. All compounds are additionally characterized by single crystal X-ray diffraction.