EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, United Kingdom.
J Am Chem Soc. 2013 May 8;135(18):7073-9. doi: 10.1021/ja402700p. Epub 2013 Apr 25.
Olefin metathesis is a powerful tool for the formation of carbon-carbon 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-indenylidene 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.
烯烃复分解反应是形成碳-碳双键的有力工具。在过去的 20 年中，已经开发出了几类明确的钌（Ru）催化剂；然而，所有此类配合物的反应机制都被假定是相同的。在本研究中，检查了 Ru-茚基配合物的引发机制，并将其与苄叉对应物进行了比较。结果发现，并非所有茚基配合物都遵循相同的机制，这突出了所谓的旁观配体的空间和电子性质的重要性，并且钌基烯烃复分解反应没有单一的机制。实验结果通过密度泛函理论（DFT）计算得到了定量支持。
