含有环己巯基配体的钨簇合物的合成及晶体结构研究

Synthesis and Crystal Structure of the Tungsten Cluster with the Cyclohexylthiolate Ligand

C6H11Na, Et4NBF4, FeCl2, (NH4)2WS4在20mL CH3OH溶剂的反应中, 标题簇合物(Et4N)3[W2Fe6S8(SC6H11)6(OCH3)3]被分离得到, 对其进行X-ray 单晶衍射和结构解析。 该化合物属正交晶系,空间群 Pmmn, 晶胞参数 a = 17.370(5), b = 15.986(4), c = 17.858(3), V = 4958.6(6)3, Z = 2,C63H135N3O3S14Fe6W2, Mr = 2134.47, Dc = 1.43g/cm3, F(000) = 2172.0, m(MoKa) = 3.49 mm-1, T = 293(2)K。 采用2966个I > 2.0s (I) 的衍射点对所有非氢原子参数进行结构修正。 得到最后的偏离因子为R = 0.072, Rw = 0.091。 这是一个双类立方烷的结构, 2个单类立方烷的端基金属钨原子通过3个甲氧基桥联。 [WFe3S4] 与 [MoFe3S4]簇核结构比较说明, 两者存在一定的相似性。

A reaction system containing C6H11Na, Et4NBF4, FeCl2 and (NH4)(2)WS4 in 20mL CH3OH solvent affords the title cluster, (Et4N)(3)[W2Fe6S8(SC6H11)(6)(OCH3)(3)]. Its crystal structure has been determined by X-ray diffiraction method. The cluster crystallizes in the orthorhombic space group Pmmm with a = 17.370(5), b = 15.986(4), c = 17.858(3)Angstrom, V=4958.6(6)Angstrom(3), Z = 2, C63H135N3O3S14Fe6W2, M-r = 2134.47, D-c = 1.36g/cm(3), F(000)=2026, mu(MoKalpha)=35.5cm(-1) and T=293(2)K. All nonhydrogen atorns were refined by using 2966 (I >2.0sigma(I)) reflections and the final refinement gave R=0.072 and Rw-0.091. The title complex is a double cubane-type structure and the tungsten atorn in each cuboidal core [WFe3S4] is bridged by three -OCH3 ligands. The comparison between the cuboidal core [WFe3S4] and the similar structure cuboidal core [MoFe3S4] indicates that both of thern are of similarity in some way.