Mechanistic comparison of ruthenium olefin metathesis catalysts: DFT insight into relative reactivity and decomposition behavior
- 作者：Werner Janse van Rensburg ; Petrus J. Steynberg ; Megan M. Kirk ; Wolfgang H. Meyer ; Grant S. Forman
- 关键词：Metathesis ; DFT ; Mechanism ; Decomposition ; Phoban catalyst
- 刊名：Journal of Organometallic Chemistry
- 出版年：2006
- 期刊代码：64_0022328x
- 类别：ch
- 出版时间：1 December 2006
- 卷：691
- 期：24-25
- 页码：5312-5325
- 文件大小：891 K
摘要
The reaction mechanism and substrate-induced decomposition behavior of three ruthenium olefin metathesis catalysts, viz. first- and second-generation catalysts and the recently developed Phoban catalyst (“Phobcat”) are compared by constructing ΔG surfaces at 298.15 K and 1 atm for the complete ligand systems. From these calculations fundamental insight is gained into the reactivity and stability observed experimentally for the three catalysts. In particular, the higher conversions obtained for the first-generation derived Phobcat catalyst, compared to conventional first-generation catalysts, is attributed to its similarity to the second-generation catalysts instead of first-generation catalyst. Important differences between the calculated ΔG surfaces and previously reported total electronic energy (ΔE) surfaces for the metathesis mechanism with complete ligand complexes are discussed.