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Issue 14, 2015
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Unexpected fragmentations of triphosphaferrocene – formation of supramolecular assemblies containing the (1,2,4-P3C2Mes2) ligand

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Abstract

While reacting the sterically demanding triphosphaferrocene [Cp*Fe(η5-P3C2Mes2)] (1) with Cu(I) halides, the sandwich complex undergoes an unprecedented fragmentation into decamethylferrocene, FeX2 (X = Cl, Br, I) and [P3C2Mes2] units. Subsequently, these phospholyl ligands act as versatile, negatively charged building blocks for the formation of supramolecular aggregates representing the monomeric, dimeric and polymeric (1D and 2D) coordination compounds [(P3C2Mes2)2{Cu7(CH3CN)74-X)(μ3-X)2(μ-X)}{Cu22-X)2X}{Cu(CH3CN)(μ2-X)}]2·6CH3CN (2·6CH3CN: X = Cl, 3·6CH3CN: X = Br), [(P3C2Mes2)2{Cu(CH3CN)}6(μ-Br)23-Br)2{Cu(CH3CN)2Br}2]·CH3CN (4a·CH3CN), [(P3C2Mes2)4{Cu5(CH3CN)52-Br)}{Cu(CH3CN)2CuBr2}2{Cu(CH3CN)2}]n+[CuBr2]n·2CH3CN (5·2CH3CN), [(P3C2Mes2){Cu(CH3CN)(μ-I)}4{Cu(CH3CN)3}]·0.5C7H8·2.5CH3CN (6·0.5C7H8·2.5CH3CN), [(P3C2Mes2)Cu7(CH3CN)44-I)23-I)2(μ-I)2]x·2C7H8 (7·2C7H8), [(P3C2Mes2){Cu(CH3CN)3}2{Cu(μ-I)}6]·0.5CH2Cl2·3CH3CN (8·0.5CH2Cl2·3CH3CN) and [Cp*Fe(CH3CN)3]n+[(P3C2Mes2)2{Cu(CH3CN)2}{Cu(μ-I)}6]n·0.6CH2Cl2 (9·0.6CH2Cl2) with rather non-typical structural motifs within the large varieties of copper halide chemistry. Besides the X-ray structural analyses the obtained assemblies were also characterized in solution in which they undergo fragmentation and re-aggregation processes.

Graphical abstract: Unexpected fragmentations of triphosphaferrocene – formation of supramolecular assemblies containing the (1,2,4-P3C2Mes2)− ligand

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Publication details

The article was received on 21 Jan 2015, accepted on 24 Feb 2015 and first published on 24 Feb 2015


Article type: Paper
DOI: 10.1039/C5DT00303B
Author version available: Download Author version (PDF)
Citation: Dalton Trans., 2015,44, 6502-6509
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    Unexpected fragmentations of triphosphaferrocene – formation of supramolecular assemblies containing the (1,2,4-P3C2Mes2) ligand

    C. Heindl, A. Kuntz, E. V. Peresypkina, A. V. Virovets, M. Zabel, D. Lüdeker, G. Brunklaus and M. Scheer, Dalton Trans., 2015, 44, 6502
    DOI: 10.1039/C5DT00303B

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