手性原子簇合物与不对称催化反应  

Framework Chirality Clusters and Asymmetric Catalysis

作　　者：殷元骐[1] 李庆山[1] 丁二润[1] 赵转云[1] 

机构地区：[1]中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室

出　　处：《分子催化》1997年第6期445-454,共10页Journal of Molecular Catalysis(China)

摘　　要：以骨架手性原子簇合物为催化剂的不对称催化反应一直被认为是极富挑战性的课题，一旦实现，将是一种理论和概念上的突破．回顾原子簇合物的不对称性及不对称催化反应的进展，阐述了我们的目标和一些相关的问题．近期实验结果表明，氧原子转移试剂Ｍｅ３ＮＯ·２Ｈ２Ｏ和ＰｈＩＯ可明显地促进异核金属羰基簇合物（μ３－Ｓ／Ｓｅ）ＲｕＣｏ２（ＣＯ）９对１－己烯的催化氢化和异构化反应．催化剂的四面体簇核骨架在催化过程中保持不变．并提出了一种可能的缔合机理．甲醇溶液中最佳条件为氢压５．０－６．０ＭＰａ，温度６０℃，［１－己烯］／［Ｓ／ＳｅＲｕＣｏ２（ＣＯ）９］为２００（摩尔比），［Ｍｅ３ＮＯ·２Ｈ２Ｏ］／［Ｓ／ＳｅＲｕＣｏ２（ＣＯ）９］为４－５（摩尔比）．The asymmetric catalysis with a framework chirality cluster as catalyst is considered to be one of the challenging subjects. Once turned to be true, it will be a breakthrough on the concept and theory. In this paper, the progress on the framework chirality clusters and the asymmetric catalysis were reviewed and our subjects, as well as the corresponding questions, were elucidated. Our recent results show that the oxygen transfer reagent, Me 3NO·2H 2O and PhIO, can promote the hydrogenation and isomerization of 1 hexene catalyzed by heterometallic carbonyl clusters, (S/Se)RuCo 2(CO) 9. The tetrahedral skeleton of the catalyst keeps intact in the catalytic process. In methanol solution, [1 Hexene]/=200, [Me 3NO·2H 2O]/=200, [Me 3NO·2H 2O]/=4, P H 2 =5.0-6.0 MPa, 60℃ and 24 h are the best reaction conditions. A plausible mechanism is proposed.

关 键 词：原子簇合物 不对称催化 不对称氢化 己烯 

分 类 号：O643.36[理学—物理化学] O623.121[理学—化学]