SiO_2负载的磺化三苯膦铑配合物催化高碳烯氢甲酰化及反应中的氘逆同位素效应  

Higher Olefin Hydrof ormylation Catalyzed by SiO_2 Supported Sulfonated-Triphenylphosphine-Rhodium-Complexes and Deuterium Inverse Isotope Effects for the Reaction

作　　者：袁友珠 刘爱民[1] 杨意泉[1] 许金来[1] 张鸿斌[1] 蔡启瑞[1] 

机构地区：[1]厦门大学化学系,物理化学研究所厦门361005

出　　处：《分子催化》1993年第6期439-445,共7页Journal of Molecular Catalysis(China)

基　　金：中国石油化工总公司基础研究基金;福建省自然科学基金资助项目

摘　　要：水溶性磺化三苯膦铑配合物担载在SiO_2表面制得的负载化水溶性Wilkinson催化剂具较大的比表面积,当1-己烯、1-辛烯、1-庚烯和十一烯酸甲酯等液态高碳烯烃在这种催化剂上于固定床加压流动态反应器中连续进行氢甲酰化催化反应时,产物醛的选择性98～100%,并可在适当过量配体存在下保持较高的催化活性.在这种催化剂上分别于CO用/H_2和CO/D_2气氛下进行烯烃氢甲酰化反应,可观察到显著的氘逆同位素效应.根据分析,初步认为酰基物中间体氢解反应可能是SiO_2负载的磺化三苯膦铑配合物催化剂上高碳烯氢甲酰化的速控步骤.Supported water-soluble Wilkinson catalysts were prepared by means of immobilizing sulfonated-triphenylphosphine-rhodium-complexes on a high surface area support of SiO2. They show an excenllent catalytic activity for the hydroformylation of liquid olefins (higher olefins), such as 1-hexene, 1-heptene, 1-octene and methyl 10-undencenoate, in a fixed bed reactor. It was found that the aldehyde selectivity was stabilized in the range of 98 - 100% and high catalytic activity was maintained even when the ligands were present in excees . Appreciable deuterium inverse isotope effects for the aldehyde formation were observed when a series of olefine hydrofomylation upon the subtitution of CO/D2 for CO/H2 was carried out to study the isotope effect of deuterium. It was believed that the kinetic isotope effect of H2/D2 coordination in the rate-determining step (RDS) was responsible for the overall inverse isotope effect. The possible RDS invovled in aldehyde formation was proposed to be the last step of formyl species hydrogenolysis.

关 键 词：催化剂 铑铬合物 烯烃 氢甲酰化 

分 类 号：O623.12[理学—有机化学]