Catalytic C-H Activation of Hydrocarbons by Rhodium(I) and Iridium(I) Complexes with Hemilabile Quinolyl-Cp Ligands

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• 作者：Gerald Kohl ; Ralph Rudolph ; Hans Pritzkow ; and Markus Enders
• 刊名：Organometallics
• 出版年：2005
• 出版时间：September 26, 2005
• 年：2005
• 卷：24
• 期：20
• 页码：4774 - 4781
• 全文大小：160K
• 年卷期：v.24,no.20(September 26, 2005)
• ISSN：1520-6041

文摘

The rhodium(I) and iridium(I) complexes 3a-6a contain the hemilabile Cp-quinolinechelate ligands 1 and 2, respectively, where the hard nitrogen donor does not displace thegood acceptor ligand ethylene. After irradiation with visible light, intensely colored complexesare obtained, where the N-donor coordinates to the metal centers. Depending on the metalatom and on the substitution pattern at the Cp rings, the mono-ethene complex with N-metalcoordination can be observed spectroscopically (e.g., 3b) or C-H addition products areprobable intermediates. The iridium complex 6a is able to activate the aliphatic C-H bondin cyclohexane. With the rhodium complex 5a as the precatalyst, catalytic H/D exchangereactions have been performed with olefinic substrates. With linear -olefins a fast double-bond isomerization dominates. The hemilabile ligands stabilize the catalytically active metalcomplexes without suppressing their activity significantly.