Cordier Stéphane, Naumov Nikolaï G, Salloum Diala, Paul Frédéric, Perrin Christiane
Laboratoire de Chimie du Solide et Inorganique Moléculaire, UMR 6511 CNRS-Université de Rennes 1, Institut de Chimie de Rennes, Avenue du Général Leclerc, 35042 Rennes Cedex, France.
Inorg Chem. 2004 Jan 12;43(1):219-26. doi: 10.1021/ic034443q.
The syntheses, crystal structures determined by single-crystal X-ray diffraction, and characterizations of new Mo(6) cluster chalcobromides and cyano-substituted compounds with 24 valence electrons per Mo(6) cluster (VEC = 24), are presented in this work. The structures of Cs(4)Mo(6)Br(12)S(2) and Cs(4)Mo(6)Br(12)Se(2) prepared by solid state routes are based on the novel (Mo(6)Br(i)(6)Y(i)(2))Br(a)(6)(-) (Y = S, Se) discrete units in which two chalcogen and six bromine ligands randomly occupy the inner positions, while the six apical ones are fully occupied by bromine atoms. The interaction of these two compounds with aqueous KCN solution results in apical ligand exchange giving the two first Mo(6) cyano-chalcohalides: Cs(0.4)K(0.6)(Et(4)N)(11)(Mo(6)Br(6)S(2))(CN)(6).16H(2)O and Cs(0.4)K(0.6)(Et(4)N)(11)(Mo(6)Br(6)Se(2))(CN)(6).16H(2)O. Their crystal structures, built from the original (Mo(6)Br(i)(6)Y(i)(2))(CN)(a)(6)(-) discrete units, will be compared to those of the two solid state precursors and other previously reported Mo(6) cluster compounds. Their redox properties and (77)Se NMR characterizations will be presented. Crystal data: Cs(4)Mo(6)Br(12)S(2), orthorhombic, Pbca (No. 61), a = 11.511(5) A, b = 18.772(5) A, c = 28.381 A (5), Z = 8; Cs(4)Mo(6)Br(12)Se(2), Pbca (No. 61), a = 11.6237(1) A, b = 18.9447(1) A, c = 28.4874(1) A, Z = 8; Cs(0.4)K(0.6)(Et(4)N)(11)(Mo(6)Br(6)S(2))(CN)(6).16H(2)O, Pm-3m (No. 221), a = 17.1969(4) A, Z = 1; Cs(0.4)K(0.6)(Et(4)N)(11)(Mo(6)Br(6)Se(2))(CN)(6).16H(2)O, Pm-3m (No. 221), a = 17.235(5) A, Z = 1.
本文介绍了新型钼（6）簇硫代溴化物和每钼（6）簇具有24个价电子（VEC = 24）的氰基取代化合物的合成、通过单晶X射线衍射测定的晶体结构以及表征。通过固态路线制备的Cs₄Mo₆Br₁₂S₂和Cs₄Mo₆Br₁₂Se₂的结构基于新型[（Mo₆Brᵢ₆Yᵢ₂）Brₐ₆]⁴⁻（Y = S，Se）离散单元，其中两个硫族元素和六个溴配体随机占据内部位置，而六个顶端位置完全被溴原子占据。这两种化合物与KCN水溶液的相互作用导致顶端配体交换，得到两种首例钼（6）氰基硫卤化物：Cs₀.₄K₀.₆（Et₄N）₁₁[（Mo₆Br₆S₂）（CN）₆]₃·16H₂O和Cs₀.₄K₀.₆（Et₄N）₁₁[（Mo₆Br₆Se₂）（CN）₆]₃·16H₂O。它们由原始的[（Mo₆Brᵢ₆Yᵢ₂）（CN）ₐ₆]⁴⁻离散单元构成的晶体结构将与两种固态前体以及其他先前报道的钼（6）簇化合物的结构进行比较。还将介绍它们的氧化还原性质和⁷⁷Se NMR表征。晶体数据：Cs₄Mo₆Br₁₂S₂，正交晶系，Pbca（编号61），a = 11.511（5）Å，b = 18.772（5）Å，c = 28.381 Å（5），Z = 8；Cs₄Mo₆Br₁₂Se₂，Pbca（编号61），a = 11.6237（1）Å，b = 18.9447（1）Å，c = 28.4874（1）Å，Z = 8；Cs₀.₄K₀.₆（Et₄N）₁₁[（Mo₆Br₆S₂）（CN）₆]₃·16H₂O，Pm - 3m（编号221），a = 17.1969（4）Å，Z = 1；Cs₀.₄K₀.₆（Et₄N）₁₁[（Mo₆Br₆Se₂）（CN）₆]₃·16H₂O，Pm - 3m（编号221），a = 17.235（5）Å，Z = 1。
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