| Title | An electronic rationale for observed initiation rates in ruthenium-mediated olefin metathesis: charge donation in phosphine and N-heterocyclic carbene ligands. |
| Publication Type | Journal Article |
| Year of Publication | 2007 |
| Authors | Getty, K, Delgado-Jaime, MUlises, Kennepohl, P |
| Journal | J. Am. Chem. Soc. |
| Volume | 129 |
| Start Page | 15774 |
| Pagination | 15774–6 |
| Date Published | dec |
| ISSN | 1520-5126 |
| ISBN Number | 0002-7863 |
| Keywords | ALKENES, Alkenes: chemistry, BOND, carbenes, CATALYSTS, CL, DFT, ELECTRONS, Heterocyclic Compounds, Heterocyclic Compounds: chemistry, HYDROCARBONS, Hydrocarbons: chemistry, KINETICS, LIGANDS, MECHANISM, METHANE, Methane: analogs & derivatives, Methane: chemistry, MOIETY, NHC LIGANDS, OLEFIN METATHESIS, phosphines, Phosphines: chemistry, RAY-ABSORPTION SPECTROSCOPY, ruthenium, Ruthenium: chemistry, TRANSITION-METAL-COMPLEXES, XAS |
| Abstract | Ru K-edge XAS data indicate that second generation ruthenium-based olefin metathesis precatalysts (L = N-heterocyclic carbene) possess a more electron-deficient metal center than in the corresponding first generation species (L = tricyclohexylphosphine). This surprising effect is also observed from DFT calculations and provides a simple rationale for the slow phosphine dissociation kinetics previously noted for second-generation metathesis precatalysts. |
| URL | <Go to ISI>://000251974000023 http://www.ncbi.nlm.nih.gov/pubmed/18047332 |
| DOI | 10.1021/ja0747674 |
