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An electronic rationale for observed initiation rates in ruthenium-mediated olefin metathesis: charge donation in phosphine and N-heterocyclic carbene ligands.

TitleAn electronic rationale for observed initiation rates in ruthenium-mediated olefin metathesis: charge donation in phosphine and N-heterocyclic carbene ligands.
Publication TypeJournal Article
Year of Publication2007
AuthorsGetty, K, Delgado-Jaime, MUlises, Kennepohl, P
JournalJ. Am. Chem. Soc.
Volume129
Start Page15774
Pagination15774–6
Date Publisheddec
ISSN1520-5126
ISBN Number0002-7863
KeywordsALKENES, 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
DOI10.1021/ja0747674