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首页> 外文期刊>Journal of chemical crystallography >Synthesis, structure and reactivity of electron deficient triosmium cluster bearing 2,6-dimethylbenzothiazolide ligand
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Synthesis, structure and reactivity of electron deficient triosmium cluster bearing 2,6-dimethylbenzothiazolide ligand

机译:含2,6-二甲基苯并噻唑化物配体的缺电子tri簇的合成,结构和反应活性

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Reaction of [Os_3(CO)10(NCMe)_2] with 2,6-dimethylbenzothiazole at room temperature affords [Os_3(CO) _(10)(μ-H){μ-η~2-C_7H_2NS(Me) _2}] (1) in 45% yield. Decarbonylation of 1 in refluxing toluene furnishes the electron-deficient cluster [Os_3(CO)_9(μ-H) {μ_3-η~2-C7H2NS (Me) _2}] (2) in almost quantitative yield. Treatment of 2 with PPh3 at 40 °C gives the addition product [Os_3(CO)_9 (PPh _3)(μ-H){μ-η~2-C_7H_2NS(Me) _2}] (3) in 85% in which the PPh3 ligand is coordinated to the rear osmium atom. A similar treatment of 2 with P(OMe)_3 gives [Os _3(CO)_9 {P(OMe)_3}(μ-H){μ- η~2-C_7H_2NS(Me)_2}] (4) in 60% yield with P(OMe)3 ligand also coordinated to the rear metal. Compounds 3 and 4 differ by the disposition of the hydride ligands. In compound 4 both the hydride and the heterocyclic ligands simultaneously bridge the same metal-metal edge whereas they bridge different metal-metal edges in 3. Compounds 1-4 have been characterized by a combination of elemental analysis, infrared, NMR and mass spectral data together with single crystal X-ray diffraction studies for 3. Compound 3 crystallizes in the monoclinic space group P2_1 with a = 9.2659(10), b = 23.643(2), c = 16.382(3) ?, β = 91.324(12)°, Z = 4 and V = 3,587.8(8) ?~3
机译:[Os_3(CO)10(NCMe)_2]与2,6-二甲基苯并噻唑在室温下反应,得到[Os_3(CO)_(10)(μ-H){μ-η〜2-C_7H_2NS(Me)_2} ](1),产率为45%。 1在回流甲苯中的脱羰作用以几乎定量的产率提供了缺电子簇[Os_3(CO)_9(μ-H){μ_3-η〜2-C7H2NS(Me)_2}](2)。在40°C下用PPh3处理2得到加成产物[Os_3(CO)_9(PPh _3)(μ-H){μ-η〜2-C_7H_2NS(Me)_2}](3),其中85% PPh3配体与后原子配位。用P(OMe)_3进行类似的2处理得到60中的[Os _3(CO)_9 {P(OMe)_3}(μ-H){μ-η〜2-C_7H_2NS(Me)_2}](4) P(OMe)3配体的%收率也与后金属配位。化合物3和4的区别在于氢化物配体的位置。在化合物4中,氢化物和杂环配体同时桥接相同的金属-金属边缘,而它们桥接3中的不同金属-金属边缘。化合物1-4通过元素分析,红外,NMR和质谱数据的组合进行了表征加上3的单晶X射线衍射研究。化合物3在单斜空间群P2_1 / n中结晶,其a = 9.2659(10),b = 23.643(2),c = 16.382(3)α,β= 91.324( 12)°,Z = 4,V = 3,587.8(8)?〜3

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