From Stoichiometric to Catalytic Binuclear Elimination in Rh鈥揥 Hydroformylations. Identification of Two New Heterobimetallic Intermediates

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• 作者：Chuanzhao Li ; Feng Gao ; Shuying Cheng ; Martin Tjahjono ; Martin van Meurs ; Boon Ying Tay ; Chacko Jacob ; Liangfeng Guo ; Marc Garland
• 刊名：Organometallics
• 出版年：2011
• 出版时间：August 22, 2011
• 年：2011
• 卷：30
• 期：16
• 页码：4292-4296
• 全文大小：824K
• 年卷期：v.30,no.16(August 22, 2011)
• ISSN：1520-6041

文摘

Cyclopentene hydroformylation, both stoichiometric and catalytic, is performed starting with Rh₄(CO)₁₂ and CpW(CO)₃H as precursors. Synergism is observed. Isotopic labeling experiments confirm 30% of the product formation occurs via a catalytic binuclear elimination reaction. Two new intermediates are spectroscopically identified using band target entropy minimization and DFT, namely, RhW(CO)₇Cp and CpW(CO)₃H-C₅H₉CORh(CO)₄. The latter intermediate appears to be hydrogen bonded via two simultaneous 畏⁵-C₅H₄鈥揌路路路O鈺怌 interactions, one with the CO group on the acyl moiety and the other with a CO on rhodium.