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

Claudia Heindl; Andrea Kuntz; Eugenia V. Peresypkina; Alexander V. Virovets; Manfred Zabel; David Lüdeker; Gunther Brunklaus; Manfred Scheer

doi:10.1039/C5DT00303B

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

Claudia Heindl,^a Andrea Kuntz,^a Eugenia V. Peresypkina,^bc Alexander V. Virovets,^bc Manfred Zabel,^a David Lüdeker,^d Gunther Brunklaus^d and Manfred Scheer*^a

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* Corresponding authors

^a Institut für Anorganische Chemie, Universität Regensburg, Universitätsstr. 31, 93053 Regensburg, Germany
E-mail: Manfred.Scheer@ur.de

^b A. V. Nikolaev Institute of Inorganic Chemistry, SB RAS, Ak. Lavrentiev prosp. 3, Novosibirsk 630090, Russia

^c Novosibirsk State University, Pirogova 2, Novosibirsk 630090, Russia

^d Institut für Physikalische Chemie, Westfälische Wilhems-Universität Münster, Corrensstr. 28, 48149 Münster, Germany

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)₇(μ₄-X)(μ₃-X)₂(μ-X)}{Cu₂(μ₂-X)₂X}{Cu(CH₃CN)(μ₂-X)}]₂·6CH₃CN (2·6CH₃CN: X = Cl, 3·6CH₃CN: X = Br), [(P₃C₂Mes₂)₂{Cu(CH₃CN)}₆(μ-Br)₂(μ₃-Br)₂{Cu(CH₃CN)₂Br}₂]·CH₃CN (4a·CH₃CN), [(P₃C₂Mes₂)₄{Cu₅(CH₃CN)₅(μ₂-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)₄(μ₄-I)₂(μ₃-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.

This article is part of the themed collection: In memory of Professor Kenneth Wade

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DOI: https://doi.org/10.1039/C5DT00303B
Article type: Paper
Submitted: 21 Jan 2015
Accepted: 24 Feb 2015
First published: 24 Feb 2015

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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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