Sulfur-Bridged Sandwich Cubane-Type Molybdenum-Antimony Cluster. Synthesis, X-ray Structure, and 121Sb Mossbauer Spectra of [(H2O)9Mo3S4SbS4Mo3(H2O)9](CH3C6H4SO3)8.24H2O

Sakane, Genta; Hashimoto, Kouichi; Takahashi, Masashi; Takeda, Masuo; Shibahara, Takashi

crystal structure molybdenum antimony sandwich cubane; structure molybdenum antimony sulfido sandwich cubane; molybdenum antimony sulfido cluster prepn structure; Mossbauer molybdenum antimony sulfido sandwich cubane; XPS molybdenum antimony sulfido sandwich cubane
A sulfur-bridged sandwich cubane-type molybdenum-antimony cluster [(H2O)9Mo3S4SbS4Mo3(H2O)9]8+ (2) was synthesized through the reaction of incomplete cubane-type molybdenum cluster [Mo3S4(H2O)9]4+ (1) with antimony metal, and was isolated as 2(pts)8.24H2O (2.pts) (Hpts = p-toluenesulfonic acid), whose structure was characterized by x-ray crystallog.  Crystal data of 2.pts: triclinic, space group P-1, a 14.468(3), b 18.531(5), c 13.713(6) angstrom, a 105.26(2), b 119.71(1), g 72.48(3)degree, Z = 1, dc = 1.696 g cm-3, Dobsd = 1.72 g cm-3, R (Rw) = 4.7 (7.5) for 6593 reflections (I > 2.0σ(I)).  The Mo-Sb distances (3.68[2] angstrom) are much longer than the Mo-Mo (2.717[7] angstrom) distances.  Peak positions and e values (λmax, nm (ε, M-1 cm-1)) of the electronic spectrum of 2.pts in 2 M HCl are 384 (13,220), 625 (10,440), and 700 (10,080).  The 121Sb Mossbauer parameters (d = -2.64 mm s-1, e2qQ = 18.1 mm s-1, h = 0.29), and the binding energies (eV) and full widths at half-max. (in parentheses, eV) obtained from XPS spectrum (Sb3d3/2, 540.3(2.3); Mo3d3/2, 233.2(2.1); Mo3d5/2, 230.2(1.9); (C1s = 285.0)) of 2.pts indicate that the oxidn. no. of antimony is III, and the mean oxidn. no. of molybdenum is +3.5.

Inorganic Chemistry

American Chemical Society

37

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