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Uncharged Selenium Rings as Terminal and Bridging Ligands in Selenium-Rich Iridium Clusters

MPG-Autoren
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Ruck,  Michael
Michael Ruck, Max Planck Fellow, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Zitation

Stolze, K., & Ruck, M. (2014). Uncharged Selenium Rings as Terminal and Bridging Ligands in Selenium-Rich Iridium Clusters. Zeitschrift für anorganische und allgemeine Chemie, 640(8-9), 1559-1563. doi:10.1002/zaac.201400092.


Zitierlink: http://hdl.handle.net/11858/00-001M-0000-0023-C9F8-A
Zusammenfassung
Purple air-stable crystals of Ir8Se40Br10 were obtained by reacting Ir in an excess of Se and SeBr4 at 300 degrees C for two weeks. The monoclinic crystal structure [space group P2(1)/c, a = 1371.9(1) pm, b = 1108.1(1) pm, c = 2058.2(1) pm, beta = 106.897(2)degrees at 296(1) K] consists of uncharged clusters Ir8Se40Br10 = (Ir3+)(8)(Se-2(2-))(Se-4(2-))(6)(Se-7)(2)(Br-)(10). The iridium(III) cations are coordinated octahedrally by selenium and bromide ions. While the oligoselenide anions provide high intra-cluster connectivity, mu(6)-eta(2) in the case of Se-2(2-) and mu(4)-eta(3) for Se-4(2-), the terminal uncharged Se-7 rings have boat conformation and are eta(1)-coordinating. About 10% of the Se-7 rings are substituted by Se-6 rings with chair conformation. A similar reaction using SeCl4 yielded vermillion air-stable crystals of Ir2Se9Cl6. X-ray diffraction on a single-crystal revealed a tetragonal lattice (space group I4(1)/a) with a = 1229.8(1) pm and c = 2365.5(2) pm at 296(1) K. In the Se-9(IrCl3)(2) cluster, a crown-shaped uncharged Se-9 ring coordinates two iridium(III) cations as a bridging bis-tridentate ligand. Three terminal chloride ions complete the distorted octahedral coordination of each transition metal atom.