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首页> 外文期刊>Organometallics >Chemistry of Unsaturated Group 6 Metal Complexes with Bridging Hydroxy and Methoxycarbyne Ligands. 5. Heterometallic Clusters Derived from the Neutral Complex [Mo-2(eta(5)-C5H5)(2)(mu-COMe)(mu-PCy2)(mu-CO)]
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Chemistry of Unsaturated Group 6 Metal Complexes with Bridging Hydroxy and Methoxycarbyne Ligands. 5. Heterometallic Clusters Derived from the Neutral Complex [Mo-2(eta(5)-C5H5)(2)(mu-COMe)(mu-PCy2)(mu-CO)]

机译：桥联羟基和甲氧卡宾配体的不饱和6族金属配合物的化学5.源自中性络合物[Mo-2（eta（5）-C5H5）（2）（mu-COMe）（mu-PCy2）（mu-CO）的杂金属簇

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The unsaturated complex [Mo2Cp2)(mu-COMe)(mu-PCy2)(mu-CO)] (1) reacts with the solvate manganese complexes [MnL(CO)(2)(THF)] (L = Cp, eta(5)-C5H4Me) rapidly at room temperature in toluene solution to give the corresponding electron-precise clusters [MnMo2Cp2L(mu(3)-COMe)(mu-PCy2)(CO)(4)] [Mo-Mo = 2.986(1) angstrom when L = Cp), which follow from the addition of the manganese fragment to compound 1 and further spontaneous carbonylation. In contrast, the incorporation of the group 8 metal fragments M(CO)(4) occurs selectively either at room temperature (reaction with [Fe-2(CO)(9)]) or under photochemical activation (reaction with [Ru-3(CO)(12)]) to give the 46-electron derivatives [Mo-2-MCp2(mu(3)-COMe)(mu-PCy2)(CO)(5)) (M = Fe, Ru), which follow from the addition of the M(CO)(4) fragment to compound 1 and carbonyl migration from M to molybdenum. Simple addition of a metal fragment to the triple intemetallic bond of 1 is observed in its reaction with CuCl, which gives the unsaturated derivative [CuMo2ClCp2(mu(3)-COMe)(mu-PCy2)(mu-CO)]. Compound 1 can also yield tetranuclear derivatives. Thus, it reacts with [Co-2(CO)(8)] at room temperature to give a mixture of the clusters [Co2Mo2-Cp-2(mu(3)-COMe)(mu-PCy2)(mu-CO)(2)(CO)(4)] and [Co2Mo2Cp2(mu(3)-COMe)(mu-PCy2)(mu-CO)(CO)(6)]. The heptacarbonyl compound has the expected composition. i.e., the one resulting from the addition of a Co-2(CO)(6) fragment to compound 1, but not the expected structure, since the PCy2 ligand is found as bridging one Mo-Co edge of the tetrahedral metal core, according to an X-ray diffraction study. In contrast, the hexacarbonyl cluster roughly has the expected structure, but has one carbonyl below the number that might have been anticipated. with the resulting unsaturation being mainly located at the Mo-Mo bond (2.686(1) angstrom) of this tetrahedral cluster.
机译：不饱和配合物[Mo2Cp2）（mu-COMe）（mu-PCy2）（mu-CO）]（1）与溶剂化锰配合物[MnL（CO）（2）（THF）]反应（L = Cp，eta（ 5）-C5H4Me）在室温下于甲苯溶液中快速生成相应的电子精确簇[MnMo2Cp2L（mu（3）-COMe）（mu-PCy2）（CO）（4）] [Mo-Mo = 2.986（1当L = Cp时）埃），其后是将锰片段添加到化合物1中并进一步自发羰基化。相比之下，第8组金属碎片M（CO）（4）的掺入选择性地在室温下（与[Fe-2（CO）（9）]反应）或在光化学活化（与[Ru-3 （CO）（12）]）得到46电子衍生物[Mo-2-MCp2（mu（3）-COMe）（mu-PCy2）（CO）（5））（M = Fe，Ru），其中然后将M（CO）（4）片段添加到化合物1中，然后羰基从M迁移到钼。在与CuCl反应中观察到金属片段简单地添加到1的三元金属键中，得到不饱和衍生物[CuMo2ClCp2（mu（3）-COMe）（mu-PCy2）（mu-CO）]。化合物1也可以产生四核衍生物。因此，它在室温下与[Co-2（CO）（8）]反应，得到簇[Co2Mo2-Cp-2（mu（3）-COMe）（mu-PCy2）（mu-CO）的混合物（2）（CO）（4）]和[Co2Mo2Cp2（mu（3）-COMe）（mu-PCy2）（mu-CO）（CO）（6）]。七羰基化合物具有预期的组成。即，根据发现，由于发现PCy2配体桥接了四面体金属核的一个Mo-Co边缘，因此将Co-2（CO）（6）片段添加到化合物1中而不是预期的结构中。进行X射线衍射研究。相反，六羰基簇大致具有预期的结构，但是具有一个羰基低于预期的数目。导致的不饱和度主要位于该四面体簇的Mo-Mo键（2.686（1）埃）处。

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