The New Binary Tungsten Iodide W15I47

The new tungsten iodide W15I47 was synthesized by reacting tungsten hexacarbonyl with iodine under elevated pressure and temperature conditions. The structure of W15I47 was refined by single-crystal X-ray diffraction with the non-centrosymmetric space group C2 [Z = 2, a = 4088.3(4) pm, b = 952.3(1) pm, c = 1198.5(2) pm, and β = 103.97(1)°]. The characteristic motif in the structure is the square pyramidal tungsten cluster that may be constructed from an octahedral [(W6I8i)I6a]2– cluster by removing one tungsten atom together with its outer iodide ligand to yield [(W5I8i)I5a]n–. The formula W15I47 represents three square pyramidal tungsten clusters with two of them being distinguishable in [(W5I8i)Ia(I3)2a(I3)2/2a–a][(W5I8i)I2a(I3)3/2a–a]2, by different numbers of iodide and tri-iodide ligands at the cluster vertices.

[1]  G. Sheldrick.  A short history of SHELX. , 2008, Acta crystallographica. Section A, Foundations of crystallography.

[2]  H. Meyer,et al.  Zwei Nitridchloride des Wolframs: W2NCl8 und W2NCl9 , 2007 .

[3]  A. J. Blake,et al.  Extended structures of polyiodide salts of transition metal macrocyclic complexes. , 2007, Acta crystallographica. Section B, Structural science.

[4]  A. Guloy,et al.  Layered organic-based metal iodide-polyiodide with unique mixed-valent gold(I/III) iodide chains. , 2004, Inorganic Chemistry.

[5]  Han‐Ki Kim,et al.  The cluster size dependence of thermal stabilities of both molybdenum and tungsten nanoclusters , 2002 .

[6]  Takehiko Mori,et al.  Organic Metal with a High Oxidation State (+5/3), (TTM-TTP)(I3)5/3. , 1997 .

[7]  J. Long,et al.  Comprehensive Tungsten-Iodine Cluster Chemistry: Isolated Intermediates in the Solid-State Nucleation of [W6I14]2- , 1995 .

[8]  D. Proserpio,et al.  MO theory made visible , 1990 .

[9]  B. Krebs,et al.  Über die Reaktion von W3O mit lod. Darstellung, Kristallstruktur und Eigenschaften von WOI3 , 1987 .

[10]  M. Binnewies.  Chemie in Glühlampen , 1986 .

[11]  H. Gray,et al.  Preparation and characterization of pentanuclear molybdenum halide clusters , 1986 .

[12]  M. Tokumoto,et al.  High Tc superconducting state in (BEDT-TTF)2 trihalides , 1985 .

[13]  H. Schäfer,et al.  Das System Wolfram/iod , 1984 .

[14]  H. Mießner,et al.  Elektronenstruktur von strukturell offenen Derivaten des [Mo6X14]2−-Clusters: [Mo5Cl13]2− und [Mo4I11]2− , 1983 .

[15]  Harald Schäufer,et al.  Bildungsmechanismus von [Mo6Cl8]Cl62− aus monomeren Ausgangsstoffen in AlCl3-haltigen Schmelzen. Isolierung des Komplexes [Mo5Cl8]Cl52− , 1977 .

[16]  H. Schäfer,et al.  [(n-C4H9)4N]2Mo5Cl13 — eine Verbindung mit der Baugruppe [Mo5Cl8i]† , 1975 .

[17]  H. Schnering,et al.  [(n‐C4H9)4N]2Mo5Cl13—A Compound with the Cluster Group [Mo5Cl i8] , 1975 .

[18]  H. Schäfer,et al.  Neue Untersuchungen über die Chloride des Molybdäns , 1967 .

[19]  F. Bolhuis,et al.  Refinement of the crystal structure of iodine at 110° K , 1967 .

[20]  R. Nyholm,et al.  Reaction of iodine with Group VI hexacarbonyls: tri-iodides of molybdenum and tungsten and their derivatives , 1966 .

[21]  H. Schäfer,et al.  Metall‐Metall‐Bindungen bei niederen Halogeniden, Oxyden und Oxydhalogeniden schwerer Übergangsmetalle Thermochemische und strukturelle Prinzipien , 1964 .