Mechanistic comparison of ruthenium olefin metathesis catalysts: DFT insight into relative reactivity and decomposition behavior
| Autor: | Grant S. Forman, Petrus J. Steynberg, Wolfgang H. Meyer, Werner Janse van Rensburg, Megan M. Kirk |
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| Rok vydání: | 2006 |
| Předmět: |
Reaction mechanism
Chemistry Ligand Organic Chemistry chemistry.chemical_element Metathesis Biochemistry Decomposition Catalysis Ruthenium Inorganic Chemistry Computational chemistry Materials Chemistry Ring-opening metathesis polymerisation Organic chemistry Reactivity (chemistry) Physical and Theoretical Chemistry |
| Zdroj: | Journal of Organometallic Chemistry. 691:5312-5325 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/j.jorganchem.2006.08.075 |
| Popis: | 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 Δ G 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 Δ G surfaces and previously reported total electronic energy (Δ E ) surfaces for the metathesis mechanism with complete ligand complexes are discussed. |
| Databáze: | OpenAIRE |
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