Ruthenium carbonyl complexes with pyridylalkanol ligands: synthesis, characterization and catalytic properties for aerobic oxidation of secondary alcohols†,New Journal of Chemistry

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Ruthenium carbonyl complexes with pyridylalkanol ligands: synthesis, characterization and catalytic properties for aerobic oxidation of secondary alcohols†
New Journal of Chemistry ( IF 2.7 ) Pub Date : 2018-03-19 00:00:00 , DOI: 10.1039/c8nj00329g
Zhiqiang Hao _{1,

2,

3,

4,

5} , Ning Li _{1,

2,

3,

4,

5} , Xinlong Yan _{1,

2,

3,

4,

5} , Ying Li _{1,

2,

3,

4,

5} , Siqi Zong _{1,

2,

3,

4,

5} , Huating Liu _{1,

2,

3,

4,

5} , Zhangang Han _{1,

2,

3,

4,

5} , Jin Lin _{1,

2,

3,

4,

5}

Affiliation

Reaction of Ru₃(CO)₁₂ with pyridylalkanol ligands PyC(CH₂)₄OH (L¹H), PyC(CH₂)₅OH (L²H) and PyCR¹R²OH (R¹ = R² = CH₃ (L³H); R¹ = CH₃, R² = C₆H₅ (L⁴H); R¹ = H, R² = C₆H₅ (L⁵H); R¹ = H, R² = 4-CH₃C₆H₄ (L⁶H); R¹ = H, R² = 4-OMeC₆H₄ (L⁷H); R¹ = H, R² = 4-ClC₆H₄ (L⁸H); R¹ = H, R² = 4-BrC₆H₄ (L⁹H); R¹ = H, R² = 4-CF₃C₆H₄ (L¹⁰H)) in refluxing xylene afforded the bis-chelate ruthenium carbonyl complexes [(Lⁿ)₂Ru₃(CO)₈] (n = 1 (1a); n = 2 (1b); n = 3 (1c); n = 4 (1d); n = 5 (1e); n = 6 (1f); n = 7 (1g); n = 8 (1h); n = 9 (1i); n = 10 (1j)), respectively. All the novel ruthenium complexes were fully characterized by NMR, elemental analyses and IR spectra and the molecular structures of 1a, 1c, 1e, 1g and 1i were further determined by single crystal X-ray diffraction analysis. In the presence of TEMPO (TEMPO = 2,2,6,6-tetramethyl-1-piperidinyloxyl), these trirhenium carbonyl clusters displayed high reactivity for aerobic oxidation of secondary alcohols to give the corresponding ketonic compounds in good to excellent yield using ambient air as the source of oxidant.

中文翻译：

具有吡啶基烷醇配体的羰基钌配合物：仲醇的好氧氧化的合成，表征和催化性能†

Ru ₃（CO）₁₂与吡啶基链烷醇配体PyC（CH ₂）₄ OH（L ¹ H），PyC（CH ₂）₅ OH（L ² H）和PyCR ¹ R ² OH（R ¹ = R ² = CH）的反应₃（L ³ H）； R ¹ = CH ₃，R ² = C ₆ H ₅（L ⁴ H）； R ¹ = H，R ² = C ₆ H ₅（L ⁵ H）；R ¹＝ H，R ²＝ 4-CH ₃ C ₆ H ₄（L ⁶ H）；R ¹＝ H，R ²＝ 4-OMeC ₆ H ₄（L ⁷ H）；R ¹＝ H，R ²＝ 4-ClC ₆ H ₄（L ⁸ H）；R ¹＝ H，R ²＝ 4-BrC ₆ H ₄（L ⁹ H）；R ¹ = H，R ² = 4-CF ₃ C在回流的二甲苯中加入₆ H₄（ L ¹⁰ H）），得到双螯合钌钌羰基配合物[（ L ⁿ）₂ Ru₃（CO）₈ ]（ n = 1（ 1a）; n = 2（ 1b）; n = 3（ 1c）; n = 4（ 1d）; n = 5（ 1e）; n = 6（ 1f）; n = 7（ 1g）; n = 8（ 1h）; n = 9（1i）; n = 10（1j））。通过NMR，元素分析和IR光谱对所有新型钌配合物进行了全面表征，并通过单晶X射线衍射分析进一步确定了1a，1c，1e，1g和1i的分子结构。在TEMPO（TEMPO = 2,2,6,6-四甲基-1-哌啶基氧基）的存在下，这些r羰基簇对仲醇的好氧氧化表现出高反应活性，从而在环境空气中以良好或极好的收率得到相应的酮化合物作为氧化剂的来源。

更新日期：2018-03-19

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