| 水溶性膦酸双核金属钌催化t-BuOOH氧化醇性能 |
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| 引用本文： | 廖海深,李辰,易小艺. 水溶性膦酸双核金属钌催化t-BuOOH氧化醇性能[J]. 无机化学学报, 2018, 34(5): 883-888 |
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| 作者姓名： | 廖海深 李辰 易小艺 |
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| 作者单位： | 中南大学化学化工学院;锰资源高效清洁利用湖南省重点实验室 |
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| 基金项目： | 国家自然科学基金（No.21571190）资助项目。 |
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| 摘 要： | 双核金属钌膦酸配合物(NH_4)_3[Ru_2(hedp)_2]·2H_2O(hedp=羟基亚乙基二膦酸)在常温水溶性体系中,无需相转移催化剂,可以高效催化t-Bu OOH氧化各种醇类,包括一级醇、二级醇和长链醇。催化机理研究表明,双核金属钌膦酸配合物的[Ru~Ⅲ-Ru~Ⅱ]~(3-)单元与t-Bu OOH作用,可以形成含过氧键的Ru~Ⅲ-Ru~Ⅲ-OO~tBu过渡态,然后再对底物醇进行氧化。该机理得到实验印证,如发现酸抑制而碱催进该反应,紫外可见光谱表明Ru~Ⅲ-Ru~Ⅲ-OO~tBu的形成。
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| 关 键 词： | 双核钌 金属-金属键 醇氧化 水溶性体系 |
| 收稿时间： | 2017-10-02 |
| 修稿时间： | 2018-01-24 |
tert-Butyl Hydroperoxide Oxygenation of Alcohol Catalyzed by Diruthenium Diphosphonate in Aqueous Solution |
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| LIAO Hai-Shen,LI Chen and YI Xiao-Yi. tert-Butyl Hydroperoxide Oxygenation of Alcohol Catalyzed by Diruthenium Diphosphonate in Aqueous Solution[J]. Chinese Journal of Inorganic Chemistry, 2018, 34(5): 883-888 |
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| Authors: | LIAO Hai-Shen LI Chen YI Xiao-Yi |
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| Affiliation: | College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China,College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China and College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China;Hunan provincial Key Laboratory of Efficient and Clear Utilization of Manganese Resources, Central South University, Changsha 410083, China |
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| Abstract: | (NH4)3[Ru2(hedp)2]·2H2O (hedp=1-hydroxyethylidenediphosphonate) with t-BuOOH as oxidant is proved to be highly effective in the catalytic oxidation of alcohol, such as secondary alcohol and long-chain aliphatic alcohol, in aqueous solution at room temperature. The phase-transfer catalyst is not necessary. The acid or the coordinated base inhibits ketone production, while the base improves the reaction selectivity and the yield. The mechanism is proposed as a peroxometal pathway. The UV-Vis spectra prove that the key intermediates Ru2-OOtBu is formed. |
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| Keywords: | dinuclear ruthenium metal-metal bond alcohol oxidation aqueous solution |
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