Rhodium(I) Ferrocenylcarbene Complexes: Synthesis, Structural Determination, Electrochemistry, and Application as Hydroformylation Catalyst Precursors

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• 作者：G. Kabelo Ramollo ; María J. López-Gómez ; David C. Liles ; Leah C. Matsinha ; Gregory S. Smith ; Daniela I. Bezuidenhout
• 刊名：Organometallics
• 出版年：2015
• 出版时间：December 28, 2015
• 年：2015
• 卷：34
• 期：24
• 页码：5745-5753
• 全文大小：431K
• ISSN：1520-6041

文摘

New examples of the rare class of rhodium(I) ferrocenyl Fischer carbene complexes 1–8, [Rh(LL)Cl{C(XR)Fc}] [LL = cod, (CO)₂, (CO, PR₃) (R = Ph, Cy or OPh), and (CO, AsPh₃); XR = OEt or NHⁿPr] were prepared, and the electronic effects of coligands and alkoxy vs aminocarbene substituents were investigated by spectroscopic and electrochemical methods. The molecular structures of complexes 1, 2, and 4–6 were confirmed by single-crystal X-ray diffraction. The use of the complexes 1–8 as homogeneous catalysts for the hydroformylation of 1-octene was demonstrated, and the influence of the carbene substituents and coligands on the activity and regioselectivity of the catalysts evaluated. Finally, the stability of the Rh–C_carbene bond of complex 1 under hydroformylation conditions was confirmed with ¹³C NMR experiments.