REACTION OF CARBON DISULFIDE WITH METAL CLUSTER CARBONYLS OF THE IRON TRIAD: SYNTHESIS AND X-RAY STRUCTURE OF (FE5(CO)13S2(CS)) CONTAINING A SIX-ELECTRON-DONOR THIOCARBONYL GROUP
REACTION OF CARBON DISULFIDE WITH METAL CLUSTER CARBONYLS OF THE IRON TRIAD: SYNTHESIS AND X-RAY STRUCTURE OF (FE5(CO)13S2(CS)) CONTAINING A SIX-ELECTRON-DONOR THIOCARBONYL GROUP
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二硫化碳与铁三元组金属簇羰基的反应：含六电子给体硫代羰基的(FE5(CO)13S2(CS))的合成和X射线结构
DOI：
10.1002/chin.198137272
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发表时间：
1981
影响因子：
4.6
通讯作者：
P. Raithby
中科院分区：
文献类型：
--
作者：
P. Broadhurst;B. Johnson;Jack Lewis;P. Raithby
已观察到硫代羰基配体 (CS) 以线性 µ,, 1 桥接 µ21, 2 和三重桥接 µ3, 模式 3 与金属中心键合（图 1a-c）。它还可以通过将碳提供给一个金属原子和将硫提供给第二个金属原子来线性桥接两个金属中心(图1d)。还有与四个金属原子配位的例子。 3, 5 在 [|(5-€ 5 5))} 3 (µ3-8)(µ3-080 (00) 5)], 3 中，Co3 三角形被碳覆盖，而硫则贡献给独立的铬中心（图 le），在 [Fe4 (CO) 12 (CS) S] 5 中，碳原子覆盖 Fe3 三角形，硫与末端键合的第四个铁原子相连到三角形 Fe3 单位（图 If）。在这些键合模式中，硫代羰基配体可以被认为向金属单元提供两个或四个电子。我们现在报道了配合物 [Fe5 (CO) l3S2 (CS)] 的制备和表征，其中已经建立了硫代羰基配体的进一步键合模式。在该络合物中，硫代羰基与排列成正方形的四个铁原子键合，并且可以正式视为六电子供体。另一个令人感兴趣的点是 Fe5 单元，它的不同寻常之处在于它包含四个铁原子的方形平面，第五个铁原子与其末端键合（图 2）。 [Fe3(CO)12]和过量CS2在己烷溶液中的反应(80℃，在10-atm CO/Ar(1:1)压力下，18小时)得到产物混合物。除去溶剂后，将混合物溶解在CH 2 Cl 2 中并使用硅胶板通过TLC分离
The thiocarbonyl ligand (CS) has been observed to bond to metal centers in the linear µ,, 1 the bridging µ21, 2 and the triply bridging, µ3, modes3 (Figure la-c). It may also bridge two metal centers linearly by donation to one metal atom from the carbon and to the second from the sulfur4 5 (Figure Id). There are also examples of coordination to four metal atoms. 3, 5 In [|(5-€ 5 5))} 3 (µ3-8)(µ3-080 (00) 5)], 3 the Co3 triangle is capped by the carbon while the sulfur donates to an independent chro-mium center (Figure le), and in [Fe4 (CO) 12 (CS) S] 5 the carbon atom caps an Fe3 triangle with the sulfur bonded to the fourth iron atom which is terminally bonded to the triangular Fe3 unit (Figure If). In these bonding modes the thiocarbonyl ligand may be considered to donate two or four electrons to the metal unit. We now report the preparation and characterization of the complex [Fe5 (CO) l3S2 (CS)] in which a further bonding mode for the thiocarbonyl ligand has been established. In this complex the thiocarbonyl group is bonded to four ironatoms arranged in a square and may be formally regarded as a six-electron donor. A further point of interest is the Fe5 unit which is unusual in that it contains a square plane of four ironatoms with the fifth iron atom terminally bonded to this (Figure 2). The reaction between [Fe3 (CO) 12] and excess CS2 in hexane solution (80 C, under a 10-atm CO/Ar (1: 1) pressure, 18 h) gave a mixture of products. After removal of the solvent, the mixture was dissolved in CH2C12 and separated by TLC using silica plates