title: On the origin of optical activity in tris-diamine complexes of Co(III) and Rh(III): a simple model based on time-dependent density function theory.
abstract: Time-dependent density functional theory (TD-DFT) is applied to the CD spectra of Lambda(deltadeltadelta)-(+)-[Co(S-pn)n(en)(3-n)]3+ (n = 1, 2, 3) and Lambda(deltadeltadelta)-(+)-[Co(en)3]3+ as well as the stereoisomers Delta-((delta)n(lambda)(3-n))-(-)-[Co(S-pn)n(en)(3-n)]3+ (n = 1, 2, 3) and Delta(deltadeltadelta)-(-)-[Co(en)3]3+. Theory is able to reproduce the major differences in the CD spectra of the species with a Lambda-configuration and their isomers with a Delta-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 Lambda-conformation compared to the Delta-configuration. Considerations were also given to the CD spectra of the lel3-isomer, Delta(lambdalambdalambda)-(-)-[Rh(R-pn)3]3+ and the ob-isomer, Lambda(lambdalambdalambda)-(+)-[Rh(S-pn)3]3+.
authors.affiliation: Department of Chemistry, University of Calgary, Calgary, Alberta, T2N-1N4, Canada.
authors.forename: Francisco Elias
authors.initials: FE
authors.lastname: Jorge
authors.forename: Jochen
authors.initials: J
authors.lastname: Autschbach
authors.forename: Tom
authors.initials: T
authors.lastname: Ziegler