四核钌-μ-氧-μ-氢氧根-氢化物配合物催化胺和羰基化合物的高效脱氢反应
Efficient Dehydrogenation of Amines and Carbonyl Compounds Catalyzed by a Tetranuclear Ruthenium-mu-Oxo-mu-Hydroxo-Hydride Complex.
作者信息
Yi Chae S, Lee Do W
机构信息
Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201-1881.
出版信息
Organometallics. 2009 Jan 29;28(4):947-949. doi: 10.1021/om8010883.
Abstract
The tetranuclear ruthenium-mu-oxo-mu-hydroxo-hydride complex {(PCy(3))(CO)RuH(mu(4)-O)(mu(3)-OH)(mu(2)-OH)} (1) was found to be a highly effective catalyst for the transfer dehydrogenation of amines and carbonyl compounds. For example, the initial turnover rate of the dehydrogenation of 2-methylindoline was measured to be 1.9 s(-1) with the TON of 7950 after 1 h at 200 degrees C. The extensive H/D scrambling patterns observed from the dehydrogenation reaction of indoline-N-d(1) and indoline-alpha-d(2) suggest a monohydride mechanistic pathway with the C-H bond activation rate-limiting step.
摘要
四核钌-μ-氧-μ-羟基-氢化物配合物{(PCy(3))(CO)RuH(μ(4)-O)(μ(3)-OH)(μ(2)-OH)} (1)被发现是胺类和羰基化合物转移脱氢反应的高效催化剂。例如，2-甲基二氢吲哚脱氢反应的初始周转速率在200℃下1小时后测得为1.9 s(-1)，TON为7950。从吲哚-N-d(1)和吲哚-α-d(2)的脱氢反应中观察到的广泛的H/D交换模式表明，其机理途径为单氢化物，其中C-H键活化是速率限制步骤。
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Thermally Stable Homogeneous Catalysts for Alkane Dehydrogenation S.O. thanks the German Academic Exchange Service (DAAD) for financing a research stay with W.C.K. in the USA. This work was supported by the National Science Foundation (CHE 9800184 to M.B.H.), by the University of California Energy Institute and University of California Santa Barbara (to W.C.K.), and by the German Research Association (DFG, to M.W.H). We thank Dr. R. Mynott and Mrs. C. Wirtz, MPI für Kohlenforschung, for NMR spectroscopic investigations.用于烷烃脱氢的热稳定均相催化剂 S.O. 感谢德国学术交流服务中心（DAAD）资助其与 W.C.K. 在美国进行研究访问。本研究得到了美国国家科学基金会（授予 M.B.H. 的 CHE 9800184 项目）、加利福尼亚大学能源研究所和加利福尼亚大学圣巴巴拉分校（授予 W.C.K.）以及德国研究协会（DFG，授予 M.W.H.）的支持。我们感谢马克斯·普朗克煤炭研究所的 R. Mynott 博士和 C. Wirtz 女士进行核磁共振光谱研究。
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