On the Origin of Optical Activity in Tris-diamine Complexes of Co(Ill) and Rh(III): A Simple Model Based on Time-Dependent Density Function Theory.
Time-dependent density functional theory (TD-DFT) is applied to the CD spectra of Λ(δδδ)-(+)-[Co(S-pn)(en)] (n = 1, 2, 3) and Λ(δδδ)-(+)-[Co(en)] as well as the stereoisomers Λ-((δ)(λ))-(-)-[Co(S-pn)(en)] (n = 1, 2, 3) and Δ(δδδ)-(-)-[Co(en)]. Theory is able to reproduce the major differences in the...
| Publicado en: | Journal of the American Chemical Society Vol. 127; no. 3; pp. 975 - 986 |
|---|---|
| Autores principales: | , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
1/26/2005
|
| 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=16053068&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 16053068 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: 1/26/2005 vid: 127 iid: 3 pid: 997 pub: American Chemical Society artinfo: ui: 16053068 10.1021/ja047670f ppf: 975 ppct: 11 formats: tig: atl: On the Origin of Optical Activity in Tris-diamine Complexes of Co(Ill) and Rh(III): A Simple Model Based on Time-Dependent Density Function Theory. aug: au: Jorge, Francisco Elias Autschbach, Jochen Ziegler, Tom affil: University of Calgary. Universidade Federal do Espirito Santo. University at Buffalo, State University of New York. su: Density functionals Cobalt Functional analysis Spectrum analysis Amines Mathematical complexes sug: subj: Density functionals Cobalt Functional analysis Spectrum analysis Amines Mathematical complexes ab: Time-dependent density functional theory (TD-DFT) is applied to the CD spectra of Λ(δδδ)-(+)-[Co(S-pn)(en)] (n = 1, 2, 3) and Λ(δδδ)-(+)-[Co(en)] as well as the stereoisomers Λ-((δ)(λ))-(-)-[Co(S-pn)(en)] (n = 1, 2, 3) and Δ(δδδ)-(-)-[Co(en)]. Theory is able to reproduce the major differences in the CD spectra of the species with a Λ-configuration and their isomers with a Δ-configuration in both the d--d and ligand-to-metal CT region. It is further possible to rationalize the trend in terms of a larger azimuthal distortion away from the octahedral geometry in the Λ-conformation compared to the Δ-configuration. Considerations were also given to the CD spectra of the lel-isomer, Δ(λλλ)-(-)-[Rh-(R-pn)] and the ob-isomer, Λ(λλλ)-(+)-[Rh(S-pn)]. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2005 holdings: @attributes: islocal: N |
|---|