4.6 Article

Hybrid Silsesquioxane/Benzoate Cu7-Complexes: Synthesis, Unique Cage Structure, and Catalytic Activity

期刊

MOLECULES
卷 27, 期 23, 页码 -

出版社

MDPI
DOI: 10.3390/molecules27238505

关键词

metallasilsesquioxanes; cagelike compounds; benzoate ligands; oxidative catalysis; alkanes; alkyl hydroperoxide

资金

  1. Russian Science Foundation [22-13-00250]
  2. Program of Fundamental Research of the Russian Federation [122040500068-0]
  3. Ministry of Education and Science of the Russian Federation
  4. ISF (Israel Science Foundation) [370/20]

向作者/读者索取更多资源

A series of phenylsilsesquioxane-benzoate heptacopper complexes were synthesized and characterized by X-ray crystallography. Complex 1 was formed through the spontaneous oxidation of toluene, while complexes 2 and 3 were obtained through directed self-assembly using benzoic acid as a reactant. Complex 3 exhibited high activity in the oxidation of alcohols.
A series of phenylsilsesquioxane-benzoate heptacopper complexes 1-3 were synthesized and characterized by X-ray crystallography. Two parallel routes of toluene spontaneous oxidation (into benzyl alcohol and benzoate) assisted the formation of the cagelike structure 1. A unique multi-ligation of copper ions (from (i) silsesquioxane, (ii) benzoate, (iii) benzyl alcohol, (iv) pyridine, (v) dimethyl-formamide and (vi) water ligands) was found in 1. Directed self-assembly using benzoic acid as a reactant afforded complexes 2-3 with the same main structural features as for 1, namely heptanuclear core coordinated by (i) two distorted pentameric cyclic silsesquioxane and (ii) four benzoate ligands, but featuring other solvate surroundings. Complex 3 was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with hydrogen peroxide and tert-butyl hydroperoxide, respectively, at 50 degrees C in acetonitrile. The maximum yield of cyclohexane oxidation products as high as 32% was attained. The oxidation reaction results in a mixture of cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone. Upon the addition of triphenylphosphine, the cyclohexyl hydroperoxide is completely converted to cyclohexanol. The specific regio- and chemoselectivity in the oxidation of n-heptane and methylcyclohexane, respectively, indicate the involvement of of hydroxyl radicals. Complex 3 exhibits a high activity in the oxidation of alcohols.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.6
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据