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首页> 外文期刊>RSC Advances >A new synthetic route for the preparation of [Os3(CO)10(μ-OH)(μ-H)] and its reaction with bis(diphenylphosphino)methane (dppm): syntheses and X-ray structures of two isomers of [Os3(CO)8(μ-OH)(μ-H)(μ-dppm)] and [Os3(CO)7(μ3-CO)(μ3-O)(μ-dppm)]
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A new synthetic route for the preparation of [Os3(CO)10(μ-OH)(μ-H)] and its reaction with bis(diphenylphosphino)methane (dppm): syntheses and X-ray structures of two isomers of [Os3(CO)8(μ-OH)(μ-H)(μ-dppm)] and [Os3(CO)7(μ3-CO)(μ3-O)(μ-dppm)]

机译：制备[OS3（Co）10（μ-OH）（μ-H）]的新的合成途径及其与双（二苯基膦基）甲烷（DPPM）的反应：[OS3]的两种异构体的合成和X射线结构（CO）8（μ-OH）（μ-H）（μ-DPPM）]和[OS3（CO）7（μ3-CO）（μ-DPPM）]]

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The triosmium cluster [Os _(3) (CO) _(10) (μ-OH)(μ-H)] containing bridging hydride and hydroxyl groups at a common Os–Os edge was obtained in good yield ( ca. 75%) from the hydrolysis of the labile triosmium cluster [Os _(3) (CO) _(10) (NCMe) _(2) ] in THF at 67 °C. [Os _(3) (CO) _(10) (μ-OH)(μ-H)] reacts with dppm at 68 °C to afford the isomeric clusters 1 and 2 with the general formula [Os _(3) (CO) _(8) (μ-OH)(μ-H)(μ-dppm)] that differ by the disposition of bridging dppm ligand. Cluster 1 is produced exclusively from the reaction of [Os _(3) (CO) _(10) (μ-OH)(μ-H)] with dppm in CH _(2) Cl _(2) at room temperature in the presence of added Me _(3) NO. Heating cluster 1 at 81 °C furnishes 2 in a process that likely proceeds by the release of one arm of the dppm ligand, followed by ligand reorganization about the cluster polyhedron and ring closure of the pendent dppm ligand. The oxo-capped [Os _(3) (CO) _(7) (μ _(3) -CO)(μ _(3) -O)(μ-dppm)] ( 3 ) has been isolated starting from the thermolysis of either 1 or 2 at 139 °C. Reactions of [Os _(3) (CO) _(10) (μ-dppm)] with ROH (R = Me, Et) in the presence of Me _(3) NO at 80 °C furnish [Os _(3) (CO) _(8) (μ-OH)(μ,η ~(1) ,κ ~(1) -OCOR)(μ-dppm)] ( 4 , R = Me; 5 , R = Et). Clusters 1–5 have been characterized by a combination of analytical and spectroscopic studies, and the molecular structure of each product has been established by X-ray crystallography. The bonding in these products has been examined by electronic structure calculations, and cluster 1 is confirmed as the kinetic product of substitution, while cluster 2 represents the thermodynamically favored isomer.
机译：含有桥接氢化物和在普通OS-OS边缘处的丙片氢和羟基的TrioSmium簇[OS _（3）（CO）_（10）（μ-OH）（μ-H）]得到良好的产量（约75％ ）在67℃下，在THF中的不稳定脂肪粒子的水解[OS _（3）（CO）_（10）（NCME）_（2）]。 [OS _（3）（CO）_（10）（μ-OH）（μ-H）]在68℃下与DPPM反应，得到异构簇1和2，通式[OS _（3）（ CO）_（8）（μ-OH）（μ-H）（μ-o-DPPM）]，其具有桥接DPPM配体的布置。专门从[OS _（3）（CO）（CO）（μ-OH）（μ-H）]在室温下与CH _（2）CL _（2）中的[OS _（3）（CO）（CO）（μ-OH）]（μ-OH）（μ-H）的反应产生的反应。添加我的存在_（3）否。在81℃下加热簇1在可能通过DPPM配体的一个臂的释放的过程中提供2，然后是关于簇多面体的配体重组和垂直DPPM配体的环闭合。氧代盖[os _（3）（co）_（7）（μ_（3）-co）（μ-_（3）-o）（μ-dppm）]（3）已经从中孤立在139℃下1或2的热解。 [os _（3）（co）_（10）（μ-dppm）的反应在ME _（3）NO在80°C提供[OS _（3 ）（CO）_（8）（μ-OH）（μ，η〜（1），κ〜（1） - 容器）（μ-dppm）]（4，r = me; 5，r = et）。簇1-5的特征在于分析和光谱研究的组合，并且通过X射线晶体学建立了每种产物的分子结构。通过电子结构计算检查了这些产品中的键合，并且簇1被证实为替代的动力学产品，而簇2代表热力学上有利的异构体。

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