Determination of the Temperature Dependence of the H--D Spin--Spin Coupling Constant and the Isotope Effect on the Proton Chemical Shift for the Compressed Dihydride Complex [Cp★Ir(P- P)H].
Complex [Cp*lr(dmpm)H] (dmpm = bis(dimethylphosphino)methane) has been reported to display temperature-dependent spin-spin coupling constant (1 ) and isotope effect on the H NMR chemical shift (Δ&delta). A combined electronic structure density functional theory + quantum nuclear dynamics study is us...
| Publicado en: | Journal of the American Chemical Society Vol. 127; no. 15; pp. 5632 - 5641 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
4/20/2005
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| 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=16827562&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 16827562 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: 4/20/2005 vid: 127 iid: 15 pid: 997 pub: American Chemical Society artinfo: ui: 16827562 10.1021/ja043011r ppf: 5632 ppct: 9 formats: tig: atl: Determination of the Temperature Dependence of the H--D Spin--Spin Coupling Constant and the Isotope Effect on the Proton Chemical Shift for the Compressed Dihydride Complex [Cp★Ir(P- P)H]. aug: au: Gelabert, Ricard Moreno, Miquel Liuch, José M. Liedos, Agusti Heinekey, D. Michael affil: Departament de Qulmica, Universitat Autbnoma de Barcelona, 08193 Bellaterra, Barcelona, Spain. Department of Chemistry, Box 351700, University of Washington, Seattle, Washington 98195-1700. su: Particles (Nuclear physics) Electronic structure Density functionals Potential energy surfaces Quantum chemistry Line geometry sug: subj: Particles (Nuclear physics) Electronic structure Density functionals Potential energy surfaces Quantum chemistry Line geometry ab: Complex [Cp*lr(dmpm)H] (dmpm = bis(dimethylphosphino)methane) has been reported to display temperature-dependent spin-spin coupling constant (1 ) and isotope effect on the H NMR chemical shift (Δ&delta). A combined electronic structure density functional theory + quantum nuclear dynamics study is used to determine from first-principles the unusual temperature dependence of the spin-spin coupling constant. It is found that the potential energy surface describing the motion of the lr-H2 unit has a deeper minimum in the dihydride region and is characterized by important anharmonicities. These anomalies affect the nature of the vibrational states of the unit and are the main reason for the unusual temperature dependence of 1 and Δ&delta. These results suggest experimental tests to identify compressed dihydride transition metal complexes. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2005 holdings: @attributes: islocal: N |
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