First Examples of Chalcofluoride Rhenium Cluster Complexes with Cubane-Like Anions [Re4Q4F12]4– (Q = S, Se)

Two rhenium tetrahedral cluster chalcofluoride compounds, K4[Re4S4F12]·3.4 H2O (1) and K4[Re4Se4F12]·6 H2O (2), have been synthesized for the first time by a reaction of Re4Q4(TeCl2)4Cl8 (Q = S, Se) with molten KHF2. Both compounds have been characterized by single-crystal X-ray diffraction methods. Compound 1 crystallizes in the trigonal space group R with 24 formula units per cell [a = b = 23.6503(3) A, c = 25.2697(7) A, V = 12240.6(4) A3 (T = 293 K)]; compound 2 crystallizes in the monoclinic space group P with four formula units per cell [a = 10.6451(3) A, b = 14.6853(4) A, c = 16.9349(5) A, α = 66.8420(10)°, β = 84.8460(10)°, γ = 85.5740(10)°, V = 2421.69(12) A3 (T = 293 K)]. Hydrophilic terminal fluoride ligands of cluster anions are included in the hydrogen bond systems of their hydrate shells. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

[1]  V. Fedorov,et al.  Coordinated bifluoride ions in the first thiofluoride molybdenum triangular cluster complex: synthesis and crystal structure of K5[Mo3S4F7(FHF)2]·2H2O , 2003 .

[2]  Thomas G. Gray.  Hexanuclear and higher nuclearity clusters of the Groups 4–7 metals with stabilizing π-donor ligands , 2003 .

[3]  V. Fedorov,et al.  Tetranuclear rhenium chalcogenide cluster complexes with a cubane core. Synthesis, structures, and properties , 2002 .

[4]  J. Gabriel,et al.  Chemistry of hexanuclear rhenium chalcohalide clusters. , 2001, Chemical reviews.

[5]  Evert Jan Baerends,et al.  Geometry optimizations in the zero order regular approximation for relativistic effects. , 1999 .

[6]  K. Kadish,et al.  Synthesis, Electrochemistry, and Imido Transfer Reactions of (TTP)Ti(η2-PhNNPh) , 1998 .

[7]  J. Ibers,et al.  Syntheses and Characterizations of the New Tetranuclear Rhenium Cluster Compounds Re4(μ3-Q)4(TeCl2)4Cl8 (Q = S, Se, Te) , 1997 .

[8]  G. Schreckenbach,et al.  Calculation of NMR Shielding Tensors Using Gauge-Including Atomic Orbitals and Modern Density Functional Theory , 1995 .

[9]  S. Jagner,et al.  On the Coordination Number of the Metal in Crystalline Halogenocuprates(I) and Halogenoargentates(I) , 1991 .

[10]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[11]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[12]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[13]  D. Russell,et al.  Potassium hexafluororhenate(IV) , 1978 .

[14]  F. L. Hirshfeld.  Bonded-atom fragments for describing molecular charge densities , 1977 .

[15]  H. Schäfer,et al.  Beiträge zur chemie der elemente niob und tantal: XLVII. Niobfluoride , 1965 .