The Activation Mechanism of Ru鈥揑ndenylidene Complexes in Olefin Metathesis

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• 作者：C茅sar A. Urbina-Blanco ; Albert Poater ; Tomas Lebl ; Simone Manzini ; Alexandra M. Z. Slawin ; Luigi Cavallo ; Steven P. Nolan
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：May 8, 2013
• 年：2013
• 卷：135
• 期：18
• 页码：7073-7079
• 全文大小：386K
• 年卷期：v.135,no.18(May 8, 2013)
• ISSN：1520-5126

文摘

Olefin metathesis is a powerful tool for the formation of carbon鈥揷arbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru鈥搃ndenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations.