Validation of the M—C/H—C Bond Enthalpy Relationship through Application of Density Functional Theory.
Density functional theory has been used to calculate HC and MC bond dissociation enthalpies in order to evaluate the feasibility of correlating relative MC bond enthalpies ΔH(MC) with HC bond enthalpies ΔH(HC) via computational methods. This approach has been tested against two experimental co...
| Publicado en: | Journal of the American Chemical Society Vol. 128; no. 25; pp. 8350 - 8358 |
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| Autores principales: | , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
6/28/2006
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=21506980&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 21506980 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 6/28/2006 vid: 128 iid: 25 pid: 997 pub: American Chemical Society artinfo: ui: 21506980 10.1021/ja061803a ppf: 8350 ppct: 8 formats: tig: atl: Validation of the M—C/H—C Bond Enthalpy Relationship through Application of Density Functional Theory. aug: au: Clot, Eric Mégret, Claire Eisenstein, Odile Perutz, Robin N. affil: LSDSMS (UMR 5636, CNRS-UM2), Institut Charles Gerhardt, Université Montpellier 2, 34095 Montpellier Cedex 5, France Department of Chemistry, University of York, York, UK YO10 5DD su: Density functionals Functional analysis Chemical bonds Organometallic chemistry Hydrocarbons Organic compounds sug: subj: Density functionals Functional analysis Chemical bonds Organometallic chemistry Hydrocarbons Organic compounds ab: Density functional theory has been used to calculate HC and MC bond dissociation enthalpies in order to evaluate the feasibility of correlating relative MC bond enthalpies ΔH(MC) with HC bond enthalpies ΔH(HC) via computational methods. This approach has been tested against two experimental correlations: a study of (a) Rh(H)(R)(Tp′)(CNCHCMe) [R = hydrocarbyl, Tp′ = HB(3,5-dimethylpyrazolyl)3] (Wick, D. D.; Jones, W. D. Organometallics 1999, 18, 495) and (b) Ti(R)(silox)(NHSit-Bu) (silox = OSit-Bu) (Bennett, J. L.; Wolczanski, P. T. J. Am. Chem. Soc. 1997, 119, 10696). We show that the observation that MC bond enthalpies increase more rapidly with different substituents than HC bond enthalpies is reproduced by theory. Quantitative slopes of the correlation lines are reproduced within 4% of the experimental values with a B3PW91 functional and with very similar correlation coefficients. Absolute bond enthalpies are reproduced within 6% for HC bonds, and relative bond enthalpies for MC bonds are reproduced within 30 kJ mol for RhC bonds and within 19 kJ mol for TiC bonds. Values are also calculated with the BP86 functional. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2006 holdings: @attributes: islocal: N |
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