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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Ligand substitution behavior of Ru6(l6-C)(CO)17 with unsaturated diphosphines: facile capping of a polyhedral face and photochemically promoted P–C bond cleavage in the cluster Ru6(l6-C)(CO)14(l3-bpcd)
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Ligand substitution behavior of Ru6(l6-C)(CO)17 with unsaturated diphosphines: facile capping of a polyhedral face and photochemically promoted P–C bond cleavage in the cluster Ru6(l6-C)(CO)14(l3-bpcd)

机译：Ru6（l6-C）（CO）17与不饱和二膦的配体取代行为：簇状Ru6（l6-C）（CO）14（l3-bpcd）中多面体表面的便捷封盖和光化学促进的P–C键裂解

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摘要

The ligand substitution chemistry of the hexaruthenium cluster Ru6 m6-C)(CO)17 (1) with several unsaturated diphosphine ligands has been investigated. Thermolysis of 1 with (Z)-Ph2PCH=CHPPh2 (dppen) furnishes the new cluster compounds Ru5(m5-C)(CO)12(m3-dppen) (2), Ru6(m6-C)(CO)14(m3-dppen) (3), and Ru6(m6-C)(CO)12(m3-dppen)(m-dppen) (4). Clusters 2 and 3 are also obtained when a mixture of 1 and dppen is treated with the oxidative-decarbonylation reagent Me3NO. Thermolysis or Me3NO activation of 1 in the presence of 4,5-bis(diphenylphosphino)-4- cyclopenten-1,3-dione (bpcd) yields Ru6(m6-C)(CO)14(m3-bpcd) (4) as the sole observable product. Near-UV irradiation of 4 leads to P–C bond cleavage and the formation of phosphido-bridged cluster Ru6(m6-C)(CO)13[m3-C=C(PPh2)C(O)CH2C(O)](m-PPh2) (6) in essentially quantitative yield. The reaction between 1 and the ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) leads to the formation of Ru6(m6-C)(CO)14(m3-bmf) (7), which exists as a single diastereomer in solution as shown by 1H and 31P NMR spectroscopy. The molecular structures and the binding mode of the ancillary diphosphine ligand(s) in 2-7 have all been established by X-ray diffraction analyses. The solid-state structure of 7 reveals that the chiral bmf ligand caps one of the metallic faces stereospecifically with the 5-methoxy moiety oriented distal or trans relative to the Ru6 polyhedral core. The new substitution products are discussed relative to the products obtained from 1 and the related diphosphine ligands dppm, dppe, dppf, and dppbz.
机译：研究了六钌簇Ru6 m6-C）（CO）17（1）与几个不饱和二膦配体的配体取代化学。 （Z）-Ph2PCH = CHPPh2（dppen）对1的热分解提供了新的簇化合物Ru5（m5-C）（CO）12（m3-dppen）（2），Ru6（m6-C）（CO）14（m3） -dppen）（3）和Ru6（m6-C）（CO）12（m3-dppen）（m-dppen）（4）。当用氧化脱羰试剂Me3NO处理1和dppen的混合物时，也会获得簇2和3。在4,5-双（二苯基膦基）-4-环戊烯-1,3-二酮（bpcd）存在下进行热解或Me3NO活化1可生成Ru6（m6-C）（CO）14（m3-bpcd）（4）作为唯一可观察的产品。近紫外辐射4导致P–C键断裂，并形成磷酸桥联簇Ru6（m6-C）（CO）13 [m3-C = C（PPh2）C（O）CH2C（O）]（ m-PPh2）（6）的定量收率。 1与配体3,4-双（二苯基膦基）-5-甲氧基-2（5H）-呋喃酮（bmf）之间的反应导致形成Ru6（m6-C）（CO）14（m3-bmf）（ 7），如1H和31P NMR光谱所示，在溶液中以单一非对映体形式存在。通过X射线衍射分析已经确定了2-7中辅助二膦配体的分子结构和结合模式。 7的固态结构表明，手性bmf配体以5-甲氧基部分相对于Ru6多面体核心朝远端或反方向立体定向地封盖了一个金属面。相对于从1和相关的二膦配体dppm，dppe，dppf和dppbz获得的产物，讨论了新的取代产物。

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