Department of Chemistry, Indian Institute of Technology Madras, Chennai 600 036, India.
Inorg Chem. 2010 Mar 15;49(6):2881-8. doi: 10.1021/ic9023597.
Vanadaborane, [(CpV)(2)(B(2)H(6))(2)] (Cp = eta(5)-C(5)H(5)), 1 reacts with elemental sulfur to afford the hexasulfide cluster [(CpV)(2)S(4)(mu-eta(1)-S(2))], 2 in high yield. Compound 2 is a notable example of an organovanadium sulfide cluster in which the [V(2)S(4)] atoms define a bicapped tetrahedron framework, with one mu-eta(1)-S(2) ligand bridged the two (CpV) moieties. The sulfur atom in [V(2)S(4)] core in 2 is a four-skeletal-electron donor isoelectronic with the BH(3) unit; therefore, the replacement of boron hydride in 1 by four sulfur atoms necessitates the formation of a bicapped tetrahedron [V(2)S(4)] framework. Furthermore, this is the only reported example of a bimetallic hexasulfide cluster containing vanadium. Pyrolysis of 1 with bis-chalcogenide ligands such as Ph(2)S(2) and Bz(2)Se(2) (Bz = PhCH(2)), results in the formation of substituted vanadahexaboranes [(CpV)(2)B(4)H(12-x)L(x)], 3-5 (3: L = SPh: x = 3; 4: L = SPh, x = 2; 5: L = SeBz: x = 1) in modest yield. All these new compounds have been characterized by mass, (1)H, (11)B, (13)C NMR spectroscopy, and elemental analysis, and the structural types were unequivocally established by crystallographic analysis of compounds 2-5.
硼烷杂多阴离子，[(CpV)(2)(B(2)H(6))(2)] (Cp = eta(5)-C(5)H(5))，1 与元素硫反应，以高产率得到六硫化物簇 [(CpV)(2)S(4)(mu-eta(1)-S(2))]，2。化合物 2 是一个显著的有机钒硫化物簇的例子，其中 [V(2)S(4)] 原子定义了一个双帽四面体框架，一个 mu-eta(1)-S(2)配体桥接两个 (CpV) 部分。2 中 [V(2)S(4)] 核心中的硫原子是四骨架电子供体与 BH(3)单元等电子；因此，在 1 中硼氢化物由四个硫原子取代，需要形成一个双帽四面体 [V(2)S(4)] 框架。此外，这是唯一报道的含有钒的双金属六硫化物簇的例子。1 与双硫属元素配体如 Ph(2)S(2) 和 Bz(2)Se(2)（Bz = PhCH(2)) 热解，生成取代的钒六硼烷 [(CpV)(2)B(4)H(12-x)L(x)]，3-5（3：L = SPh：x = 3；4：L = SPh，x = 2；5：L = SeBz：x = 1)，产率适中。所有这些新化合物都通过质谱、(1)H、(11)B、(13)C NMR 光谱和元素分析进行了表征，并通过化合物 2-5 的晶体结构分析明确确立了结构类型。
