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Coordination Chemistry of [CpFe(η5-P3C2tBu2)] (Cp =η5-C5Me5) with Copper(I) Halides - Formation of Oligomeric and Polymeric Compounds

Schindler, Andrea and Balázs, Gábor and Zabel, Manfred and Gröger, Christian and Kalbitzer, Hans Robert and Scheer, Manfred (2010) Coordination Chemistry of [Cp*Fe(η5-P3C2tBu2)] (Cp* =η5-C5Me5) with Copper(I) Halides - Formation of Oligomeric and Polymeric Compounds. Comptes Rendus Chimie 13 (8-9), pp. 1241-1248.

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Abstract

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.