Reactions of 1,1'-Diphosphaferrocene with CuCl and CuBr Resulting in Cu4P4X4Fe2 (X = Cl, Br) Complexes with Adamantane-like Topologies

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2010
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Schnödt, Johannes
Zabel, Manfred
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Zeitschrift für anorganische und allgemeine Chemie. 2010, 636(7), pp. 1242-1248. eISSN 0044-2313. Available under: doi: 10.1002/zaac.200900588
Zusammenfassung

Cu4P4X4Fe2 (X = Cl, Br) cages are formed upon reactions of octaethyl-1,1′-diphosphaferrocene (odpf) with the respective CuI halide in CH2Cl2/CH3CN solvent mixtures. These cages have adamantoid Cu4X4P2 cores with two planar anelated CuP2Fe rings as the flaps. Both complexes 1 and 2 feature tri- and tetracoordinate CuI ions and an additional acetonitrile solvent molecule in the crystal. In 1, the solvent molecule is coordinated to one copper ion whereas it remains uncoordinated in 2. The tricoordinate CuI ions show a slight pyramidalization at the metal atom and somewhat short contacts to the other tricoordinate CuI ion in 2 or the Cu3-triangle in 1. NMR spectroscopy revealed easy decoordination of the acetonitrile ligand from 1 and a dynamic “windshield-wiper”-type process that interconverts the differently coordinated phospholide rings of each odpf ligand and the tri- and tetracoordinate CuI ions.

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540 Chemie
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Copper, 1,1'-Diphosphaferrocene, Diphosphanes, Chlorine, Bromine, Cage compounds
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ISO 690SCHNÖDT, Johannes, Rainer F. WINTER, Manfred ZABEL, 2010. Reactions of 1,1'-Diphosphaferrocene with CuCl and CuBr Resulting in Cu4P4X4Fe2 (X = Cl, Br) Complexes with Adamantane-like Topologies. In: Zeitschrift für anorganische und allgemeine Chemie. 2010, 636(7), pp. 1242-1248. eISSN 0044-2313. Available under: doi: 10.1002/zaac.200900588
BibTex
@article{Schnodt2010React-9655,
  year={2010},
  doi={10.1002/zaac.200900588},
  title={Reactions of 1,1'-Diphosphaferrocene with CuCl and CuBr Resulting in Cu<sub>4</sub>P<sub>4</sub><em>X</em><sub>4</sub>Fe<sub>2</sub> (X = Cl, Br) Complexes with Adamantane-like Topologies},
  number={7},
  volume={636},
  journal={Zeitschrift für anorganische und allgemeine Chemie},
  pages={1242--1248},
  author={Schnödt, Johannes and Winter, Rainer F. and Zabel, Manfred}
}
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    <dcterms:abstract xml:lang="eng">Cu&lt;sub&gt;4&lt;/sub&gt;P&lt;sub&gt;4&lt;/sub&gt;&lt;em&gt;X&lt;/em&gt;&lt;sub&gt;4&lt;/sub&gt;Fe&lt;sub&gt;2&lt;/sub&gt; (&lt;em&gt;X&lt;/em&gt; = Cl, Br) cages are formed upon reactions of octaethyl-1,1&amp;#8242;-diphosphaferrocene (odpf) with the respective Cu&lt;sup&gt;I&lt;/sup&gt; halide in CH&lt;sub&gt;2&lt;/sub&gt;Cl&lt;sub&gt;2&lt;/sub&gt;/CH&lt;sub&gt;3&lt;/sub&gt;CN solvent mixtures. These cages have adamantoid Cu&lt;sub&gt;4&lt;/sub&gt;&lt;em&gt;X&lt;/em&gt;&lt;sub&gt;4&lt;/sub&gt;P&lt;sub&gt;2&lt;/sub&gt; cores with two planar anelated CuP&lt;sub&gt;2&lt;/sub&gt;Fe rings as the flaps. Both complexes &lt;b&gt;1&lt;/b&gt; and &lt;b&gt;2&lt;/b&gt; feature tri- and tetracoordinate Cu&lt;sup&gt;I&lt;/sup&gt; ions and an additional acetonitrile solvent molecule in the crystal. In &lt;b&gt;1&lt;/b&gt;, the solvent molecule is coordinated to one copper ion whereas it remains uncoordinated in &lt;b&gt;2&lt;/b&gt;. The tricoordinate Cu&lt;sup&gt;I&lt;/sup&gt; ions show a slight pyramidalization at the metal atom and somewhat short contacts to the other tricoordinate Cu&lt;sup&gt;I&lt;/sup&gt; ion in &lt;b&gt;2&lt;/b&gt; or the Cu&lt;sub&gt;3&lt;/sub&gt;-triangle in &lt;b&gt;1&lt;/b&gt;. NMR spectroscopy revealed easy decoordination of the acetonitrile ligand from &lt;b&gt;1&lt;/b&gt; and a dynamic “windshield-wiper”-type process that interconverts the differently coordinated phospholide rings of each odpf ligand and the tri- and tetracoordinate Cu&lt;sup&gt;I&lt;/sup&gt; ions.</dcterms:abstract>
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