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

Francisco Elias Jorge; Jochen Autschbach; Tom Ziegler

doi:10.1021/ja047670f

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

Francisco Elias Jorge
, Jochen Autschbach
, Tom Ziegler

Chemistry

University of Calgary
Universidade Federal do Espírito Santo

Research output: Contribution to journal › Article › peer-review

82 Scopus citations

Abstract

Time-dependent density functional theory (TD-DFT) is applied to the CD spectra of Λ(δδδ)-(+)-[Co(S-pn)_n(en) _3-n]³⁺ (n = 1, 2, 3) and Λ(δδδ)- (+)-[Co(en)₃]₃₊ as well as the stereoisomers Δ-((δ)_n(γ)_3-n)-(-)-[Co(S-pn) _n(en)_3-n]³⁺ (n = 1, 2, 3) and Δ(δδδ)-(-)-[Co(en)₃]³⁺. 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 lel₃-isomer, Δ(γγγ)-(-)-[Rh-(R-pn)₃]³⁺ and the ob-isomer, Λ(γγγ)-(+)-[Rh(S-pn)₃] ³⁺.

Original language	English
Pages (from-to)	975-985
Number of pages	11
Journal	Journal of the American Chemical Society
Volume	127
Issue number	3
DOIs	https://doi.org/10.1021/ja047670f
State	Published - Jan 26 2005

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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 Λ(δδδ)-(+)-[Co(S-pn)n(en) 3-n]3+ (n = 1, 2, 3) and Λ(δδδ)- (+)-[Co(en)3]3+ as well as the stereoisomers Δ-((δ)n(γ)3-n)-(-)-[Co(S-pn) n(en)3-n]3+ (n = 1, 2, 3) and Δ(δδδ)-(-)-[Co(en)3]3+. 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 lel3-isomer, Δ(γγγ)-(-)-[Rh-(R-pn)3]3+ and the ob-isomer, Λ(γγγ)-(+)-[Rh(S-pn)3] 3+.",

author = "Jorge, \{Francisco Elias\} and Jochen Autschbach and Tom Ziegler",

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T2 - A simple model based on time-dependent density function theory

AU - Jorge, Francisco Elias

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AU - Ziegler, Tom

PY - 2005/1/26

Y1 - 2005/1/26

N2 - Time-dependent density functional theory (TD-DFT) is applied to the CD spectra of Λ(δδδ)-(+)-[Co(S-pn)n(en) 3-n]3+ (n = 1, 2, 3) and Λ(δδδ)- (+)-[Co(en)3]3+ as well as the stereoisomers Δ-((δ)n(γ)3-n)-(-)-[Co(S-pn) n(en)3-n]3+ (n = 1, 2, 3) and Δ(δδδ)-(-)-[Co(en)3]3+. 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 lel3-isomer, Δ(γγγ)-(-)-[Rh-(R-pn)3]3+ and the ob-isomer, Λ(γγγ)-(+)-[Rh(S-pn)3] 3+.

AB - Time-dependent density functional theory (TD-DFT) is applied to the CD spectra of Λ(δδδ)-(+)-[Co(S-pn)n(en) 3-n]3+ (n = 1, 2, 3) and Λ(δδδ)- (+)-[Co(en)3]3+ as well as the stereoisomers Δ-((δ)n(γ)3-n)-(-)-[Co(S-pn) n(en)3-n]3+ (n = 1, 2, 3) and Δ(δδδ)-(-)-[Co(en)3]3+. 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 lel3-isomer, Δ(γγγ)-(-)-[Rh-(R-pn)3]3+ and the ob-isomer, Λ(γγγ)-(+)-[Rh(S-pn)3] 3+.

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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

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