Probing the Solvent Shell with Pt Chemical Shifts: Density Functional Theory Molecular Dynamics Study of Pt and Pt Anionic Complexes in Aqueous Solution.
Ab initio molecular dynamics (aiMD) simulations based on density functional theory (OFT) were performed on a set of five anionic platinum complexes in aqueous solution. pt nuclear magnetic shielding constants were computed with DFT as averages over the aiMD trajectories, using the two-component rela...
| Publicado en: | Journal of the American Chemical Society Vol. 132; no. 10; pp. 3472 - 3484 |
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| Autores principales: | , |
| Formato: | Artículo |
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American Chemical Society
3/17/2010
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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=48808416&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 48808416 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: 3/17/2010 vid: 132 iid: 10 pid: 997 pub: American Chemical Society artinfo: ui: 48808416 10.1021/ja9096863 ppf: 3472 ppct: 12 formats: tig: atl: Probing the Solvent Shell with Pt Chemical Shifts: Density Functional Theory Molecular Dynamics Study of Pt and Pt Anionic Complexes in Aqueous Solution. aug: au: Truflandier, Lionel A. Autschbach, Jochen affil: Department of Chemistry, 312 Natural Sciences Complex, State University of New York, Buffalo, New York 14260-3000 su: Density functionals Platinum Molecular dynamics Anions Magnetic shielding Zeroth law of thermodynamics Calculus of tensors sug: subj: Density functionals Platinum Molecular dynamics Anions Magnetic shielding Zeroth law of thermodynamics Calculus of tensors ab: Ab initio molecular dynamics (aiMD) simulations based on density functional theory (OFT) were performed on a set of five anionic platinum complexes in aqueous solution. pt nuclear magnetic shielding constants were computed with DFT as averages over the aiMD trajectories, using the two-component relativistic zeroth-order regular approximation (ZORA) in order to treat relativistic effects on the Pt shielding tensors. The chemical shifts obtained from the aiMD averages are in good agreement with experimental data. For Pt(II) and Pt(IV) halide complexes we found an intermediate solvent shell interacting with the complexes that causes pronounced solvent effects on the Pt chemical shifts. For these complexes, the magnitude of solvent effects on the Pt shielding constant can be correlated with the surface charge density. For square-planar Pt complexes the aiMD simulations also clearly demonstrate the influence of closely coordinated non-equatorial water molecules on the Pt chemical shift, relating the structure of the solution around the complex to the solvent effects on the metal NMR chemical shift. For the complex [Pt(CN)], the solvent effects on the Pt shielding constant are surprisingly small. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
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