水溶性膦酸双核金属钌催化t-BuOOH氧化醇性能

摘要

双核金属钌膦酸配合物(NH4)3[Ru2(hedp)2]·2H2O(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-BuOOH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[RuⅢ-RuⅡ]3-单元与t-BuOOH作用,可以形成含过氧键的RuⅢ-RuⅢ-OOtBu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RuⅢ-RuⅢ-OOtBu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.