水溶性膦酸双核金属钌催化t-BuOOH氧化醇性能  

tert-Butyl Hydroperoxide Oxygenation of Alcohol Catalyzed by Diruthenium Diphosphonate in Aqueous Solution

作　　者：廖海深 李辰 易小艺[1,2] LIAO Hai-Shen;LI Chen;YI Xiao-Yi(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)

机构地区：[1]中南大学化学化工学院,长沙410083 [2]锰资源高效清洁利用湖南省重点实验室,长沙410083

出　　处：《无机化学学报》2018年第5期883-888,共6页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21571190)资助项目

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。(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.

关 键 词：双核钌 金属-金属键 醇氧化 水溶性体系 

分 类 号：O643[理学—物理化学] O614.821[理学—化学]