The tris-(R)-()-propylenediamine complexes of rhodium(III)

HEARSON, J. A.; Mason, S. F.; Wood, J. W. M.

doi:10.1016/s0020-1693(00)94747-9

Cited by 8 publications

(9 citation statements)

References 11 publications

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“…The relative magnitudes of the rotatory strengths for these transitions, and their energies, depend slightly on the ob or lel conformation of the chelate ring. It is expected that the negative CD band β results from the spectrum of the lel conformations; − therefore its absence in the simulated ob 3 conformer spectrum is in agreement with the experimental data. We will investigate this issue in more detail in a subsequent publication…”

Section: Resultsmentioning

confidence: 92%

Density Functional Calculations on Electronic Circular Dichroism Spectra of Chiral Transition Metal Complexes

2003

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Time-dependent density functional theory (TD-DFT) has for the first time been applied to the computation of circular dichroism (CD) spectra of transition metal complexes, and a detailed comparison with experimental spectra has been made. Absorption spectra are also reported. Various Co(III) complexes as well as [Rh(en)(3)](3+) are studied in this work. The resulting simulated CD spectra are generally in good agreement with experimental spectra after corrections for systematic errors in a few of the lowest excitation energies are applied. This allows for an interpretation and assignment of the spectra for the whole experimentally accessible energy range (UV/vis). Solvent effects on the excitations are estimated via inclusion of a continuum solvent model. This significantly improves the computed excitation energies for charge-transfer bands for complexes of charge +3, but has only a small effect on those for neutral or singly charged complexes. The energies of the weak d-to-d transitions of the Co complexes are systematically overestimated due to deficiencies of the density functionals. These errors are much smaller for the 4d metal complex. Taking these systematic errors and the effect of a solvent into consideration, TD-DFT computations are demonstrated to be a reliable tool in order to assist with the assignment and interpretation of CD spectra of chiral transition metal complexes.

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Section: Resultsmentioning

confidence: 92%

Density Functional Calculations on Electronic Circular Dichroism Spectra of Chiral Transition Metal Complexes

2003

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“…The CD Spectra of the lel 3 -Isomer, Δ(λλλ)-(−)-[Rh(R-pn) 3 ] 3+ , the ob -Isomer, Λ(λλλ)-(+)-[Rh(S-pn) 3 ] 3+ . Figure displays the absorption and CD spectra of the lel 3 -system, Δ(λλλ)-(−)-[Rh(R-pn) 3 ] 3+ and the ob 3 -stereoisomer, Λ(λλλ)-(+)-[Rh(R-pn) 3 ] 3+ obtained from TD-DFT and experimental data …”

Section: Resultsmentioning

confidence: 99%

“…In the present work, TD-DFT is employed to simulate the absorption and CD spectra of Λ-[Co(S-pn) n (en) 3 - n ] 3+ , Δ-[Co(S-pn) n (en) 3 - n ] 3+ ( n = 1, 2, 3), Λ-[Co(en) 3 ] 3+ , Δ-[Co(en) 3 ] 3+ , Λ-[Rh(R-pn) 3 ] 3+ , and Δ-[Rh(R-pn) 3 ] 3+ . These data are compared with the corresponding experimental spectra. , We have chosen these systems because of the available experimental data and because Λ-[Co(S-en) n (en) 3 - n ] 3+ and Δ-[Co(S-pn) n (en) 3 - n ] 3+ ( n = 1, 2, 3) as well as Λ-[Rh(R-pn) 3 ] 3+ and Δ-[Rh(R-pn) 3 ] 3+ have the potential to form pairs of diastereoisomers according to the discussion above. By comparing their CD spectra it is thus possible to study the configurational and conformational effects observed in CD spectra of Co(III) tris-diamine complexes for both d−d and CT transitions through the different influence exerted by diamine chains in their ob - and lel -conformations.…”

Section: Introductionmentioning

confidence: 99%

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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

2004

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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+.

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“…The authors compare their theoretical results to the available experimental ECD spectra. 140,141 They also compare the theoretical spectrum of the energetically unfavored ob 3 form to the experimental and theoretical ECD of the lel 3 form. The energetically low-lying ECD bands are dominated by d → d type transitions, whereas ECD transitions from the central metal ion to the ligands are present in the high-energy region.…”

Section: Stereochemistry Of Transition Metal Complexesmentioning

confidence: 99%

Circular dichroism: electronic

Warnke

Furche

2011

WIREs Comput Mol Sci

126

137

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First‐principles calculations of electronic circular dichroism (ECD) are widely used to determine absolute configurations of chiral molecules. In addition, ECD is a sensitive probe for the three‐dimensional molecular structure, making ECD calculations a useful tool to study conformational changes. In this review, we explain the origin of ECD and optical activity using response theory. While the quantum‐mechanical underpinnings of ECD have been known for a long time, efficient electronic structure methods for ECD calculations on molecules with more than 10–20 atoms have become widely available only in the past decade. We review the most popular methods for ECD calculation, focusing on time‐dependent density functional theory. Although single‐point vertical ECD calculations yield useful accuracy for conformationally rigid systems, inclusion of finite‐temperature effects is necessary for flexible molecules. The scope and limitations of modern ECD calculations are illustrated by applications to helicenes, fullerenes, iso‐schizozygane alkaloids, paracyclophanes, β‐lactams, and transition metal complexes. © 2011 John Wiley & Sons, Ltd. WIREs Comput Mol Sci 2011 00 1–17 DOI: 10.1002/wcms.55 This article is categorized under: Electronic Structure Theory > Density Functional Theory

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The tris-(R)-()-propylenediamine complexes of rhodium(III)

Cited by 8 publications

References 11 publications

Density Functional Calculations on Electronic Circular Dichroism Spectra of Chiral Transition Metal Complexes

Density Functional Calculations on Electronic Circular Dichroism Spectra of Chiral Transition Metal Complexes

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

Circular dichroism: electronic

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