【摘要】 本文报道具有松散配位的三核钼簇合物{Mo₃（μ₃-S）（μ-S）₃[S₂P（OEt）₂]₄·L’（L’=H₂O,1;C₃H₃ON,2）和SbCl₃在HCl-EtOH中的加合反应及其产物{Mo₃（μ₃-S）[（μ-S）₃·SbCl₃]·[S₂P（OEt）₂]₄（C₂H₅OH）}（C₂H₅OH）（3）和{Mo₃（μ₃-S）[（μ-S）₃·SbCl₃][S₂P（OEt）₂]₃[SXP（OEt）₂]·（C₃H₃ON）}（X=S,O）（4）的晶体结构.晶体3空间群属P2₁/n,晶胞参数为α=13.250（3）,6=17.296（4）,c=23.223（9）A,β=92.4l（3）°,D_?=1.844g·cm^-3;晶体4空间群属PI,晶胞参数为α=10.342（3）,b=11.994（3）,c=21.352（4）A,α=76.27（2）,β=88.55（2）,γ=73.26（2）°,D₌1.947g·cm^-3.晶体3、4的最终结构偏离因子分别为0.078和0.068.结构测定结果表明,这两个加合物的分子由{Mo₃（μ₃-S）（μ-S）₃[S₂P（OEt）₂]₄·L（L=C₂H₅OH,C₃H₃ON）通过三个（μ-S）联结SbCl₃而成,从而获得了{Mo₃SbS₄}的类立方烷簇胳构型,Sb—S之间存在较弱的配位键.由此推断,若加合的金属原子的轨道和电子组态适宜,有可能通过这种[3+1]的成簇模式获得四核的同核或异核簇合物.更多还原

【Abstract】 The additive reaction of SbCl₃ to trimolybdenum clusters with loose coordination sites, Mo₃（μ₃-S）（μ-S）₃[S₂P（OEt）₂]₄-L’ （1, L’=H₂O, 2, L’=C₃H₃ON）, in a C₂H₅OH/C₂H₅OH-HCl medium yields compounds {Mo₃-S) [（μ-S）₃·SbCl₃] [S₂P（OEt）₂]₄·（C₂H₅OH）}（C₂H₅OH） （3） and {Mo₃（μ₃-S） [（μ-S）₃·SbCl₃] [S₂P（OEt）₂]₃ [SXP（OEt）₂]·（C₃H₃ON）}（X=S, O）（4）, respectively. The crystal and molecular structures of these two compounds have been determined by single orystal X-ray crystallography: crystal 3 belongs to the monoclinic system, P2_1/n, with cell dimensions: a=13.250 （3）, b=17.296 （4）, c=23.223（9）A, β=92.41（3）°, Z=4; while crystal 4 belongs to the triclinic system, P1, with cell dimensions: a=10.342（3）, b=11.994（3）, c=21.352（4）A, α=76.27（2）,β=88.55（2）, γ=73.26（2）°, Z=2, The intensity data were collected on an Enraf-Nonius CAD-4 diffractometer with graphite-monochromatized Mo Kα radiation by using the ω-2θ teohnique. 2054 reflections with I≥2σ（I） were obtained for crystal 3; 4035 with I≥3σ（I） for crystal 4. The structures were solved by the Patterson method as well as direct methods and refined by full matrix least-squares method. Final R values were 0.078 for crystal 3 and 0.068 for crystal 4, respectively. The result of the structure determination showed that the two molecular structures are practically formed by connecting a trimolybdenum clusters with loose coordination sites, {Mo₃（μ₃-S）（μ-S）₃ [S₂P（OEt）₂]₄·L（L=C₂H₅OH, C₃H₃ON）, with a SbCl₃ molecule through three （μ-S） atoms to form the {Mo₃SbS₄} core of a cubane-like type. There are relatively weak coordination bonds between bhe Sb and the three （μ-S） atoms, while no bondinginteraction between the Sb and the three Mo atoms is found. In the additive compounds the structural character of the trimolybdenum clusters with loose coordination sites has not been significantly changed. In addition, crystal 3 still has the reactivity for the loosely coordinated EtOH to be replaced by an oxazole ring to form crystal 4. However, as a result of the addition, the three （μ-S） atoms may be regarded as triple bridging S atorng each connecting two Mo atoms and a Sb atom. The information obtained in the structural analysis serves as an evidence that the tetranuclear clusters might be formed by a [3+1] reaction mode.更多还原