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

An electronic rationale for observed initiation rates in ruthenium-mediated olefin metathesis: charge donation in phosphine and N-heterocyclic carbene ligands. Getty, K., Delgado-Jaime, M., U., & Kennepohl, P. J. Am. Chem. Soc., 129(51):15774-6, 12, 2007.

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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.

@article{
 title = {An electronic rationale for observed initiation rates in ruthenium-mediated olefin metathesis: charge donation in phosphine and N-heterocyclic carbene ligands.},
 type = {article},
 year = {2007},
 keywords = {DFT,SSRL,X-ray Absorption Spectroscopy,carbenes,olefin metathesis},
 pages = {15774-6},
 volume = {129},
 websites = {http://www.ncbi.nlm.nih.gov/pubmed/18047332},
 month = {12},
 day = {26},
 chapter = {15774},
 id = {2af4b1d4-b450-3874-b3a6-4945d0010372},
 created = {2017-09-06T15:14:52.714Z},
 accessed = {2011-11-03},
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 profile_id = {8c5f55f8-b69e-30e2-981b-01f0d567bbfe},
 last_modified = {2017-09-06T15:21:20.406Z},
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 citation_key = {ISI:000251974000023},
 source_type = {article},
 language = {English},
 notes = {<b>From Duplicate 1 ( </b><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><b><br/><br/><br/><br/><br/><br/><br/></b><br/><b><br/><i>An electronic rationale for observed initiation rates in ruthenium-mediated olefin metathesis: Charge donation in phosphine and N-heterocyclic carbene ligands</i><br/></b><br/><b><br/><br/><br/><br/><br/><br/><br/></b><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><b>- Getty, Kendra; Delgado-Jaime, Mario Ulises; Kennepohl, Pierre )<br/><br/><br/><br/><br/><br/><br/><br/></b><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><b>From Duplicate 1 ( </b><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><b><br/><br/><br/><br/><br/><br/><br/></b><br/><b><br/><i>An electronic rationale for observed initiation rates in ruthenium-mediated olefin metathesis: Charge donation in phosphine and N-heterocyclic carbene ligands</i><br/></b><br/><b><br/><br/><br/><br/><br/><br/><br/></b><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><br/><b>- Getty, K; Delgado-Jaime, M U; Kennepohl, P )<br/><br/><br/><br/><br/><br/><br/><br/></b><br/><br/><br/><br/><br/><br/><br/><br/>ISI Document Delivery No.: 245YF<br/>Times Cited: 4<br/>Cited Reference Count: 40<br/>Getty, Kendra Delgado-Jaime, Mario Ulises Kennepohl, Pierre<br/>AMER CHEMICAL SOC},
 folder_uuids = {78605f3e-c4ca-4aa1-bb27-8876e9306d5d},
 private_publication = {false},
 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.},
 bibtype = {article},
 author = {Getty, Kendra and Delgado-Jaime, Mario Ulises and Kennepohl, Pierre},
 doi = {10.1021/ja0747674},
 journal = {J. Am. Chem. Soc.},
 number = {51}
}

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