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An Ionic Liquid Based Single Step Room Temperature Route for the Synthesis of Molybdenum Cluster Compounds
Author(s) -
Ahmed Ejaz,
Ahrens Eike,
Heise Martin,
Ruck Michael
Publication year - 2011
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201000428
Subject(s) - ionic liquid , molybdenum , bismuth , chemistry , monoclinic crystal system , octahedron , cluster (spacecraft) , square pyramid , crystallography , ionic bonding , inorganic chemistry , chloride , ion , crystal structure , catalysis , organic chemistry , computer science , programming language
A soft and convenient single step route is developed to synthesize molybdenum cluster compounds using an ionic liquid as reaction medium. Bi[Mo 5 Cl 13 ]Cl and [BiCl][Mo 6 Cl 14 ] were isolated from the ionic liquid [BMIM]Cl/AlCl 3 ([BMIM] + : 1‐ n ‐butyl‐3‐methylimidazolium) and characterized. Black, cubic crystals of Bi[Mo 5 Cl 13 ]Cl are obtained at room temperature by the reaction of bismuth, BiCl 3 , and MoCl 5 in Lewis‐acidic ionic liquid [BMIM]Cl/AlCl 3 . Bi[Mo 5 Cl 13 ]Cl crystallizes in the cubic space group Pn $\bar{3}$ with a = 1291.6(3) pm. In the [Mo 5 Cl 13 ] 2– cluster, the molybdenum atoms form a square pyramid with Mo–Mo bond lengths 258.9(2) pm and 259.5(2) pm. The structure is a defect variant of the Pb[Mo 6 Cl 14 ] type; in statistical distribution one of the molybdenum atoms is missing in the cluster core. The bismuth(III) cations, which are in octahedral coordination by the apical chloride ions of the clusters, connect the cluster anions into a three dimensional network. Light red crystals of monoclinic [BiCl][Mo 6 Cl 14 ] were obtained by the oxidation of bismuth with MoCl 5 in [BMIM]Cl/AlCl 3 . The structure determination is in excellent agreement with literature data of crystals obtained by high temperature syntheses.