The importance of relativistic effects for carbon as an NMR reporter nucleus in carbide bridged [RuCPt]-complexes

Research output: Contribution to journal › Journal article › Research › peer-review

Standard

The importance of relativistic effects for carbon as an NMR reporter nucleus in carbide bridged [RuCPt]-complexes. / Glent-Madsen, Iben; Reinholdt, Anders; Bendix, Jesper; Sauer, Stephan P. A.

In: Organometallics, Vol. 40, No. 10, 24.05.2021, p. 1443-1453.

Research output: Contribution to journal › Journal article › Research › peer-review

Harvard

Glent-Madsen, I, Reinholdt, A, Bendix, J & Sauer, SPA 2021, 'The importance of relativistic effects for carbon as an NMR reporter nucleus in carbide bridged [RuCPt]-complexes', Organometallics, vol. 40, no. 10, pp. 1443-1453. https://doi.org/10.1021/acs.organomet.1c00079

APA

Glent-Madsen, I., Reinholdt, A., Bendix, J., & Sauer, S. P. A. (2021). The importance of relativistic effects for carbon as an NMR reporter nucleus in carbide bridged [RuCPt]-complexes. Organometallics, 40(10), 1443-1453. https://doi.org/10.1021/acs.organomet.1c00079

Vancouver

Glent-Madsen I, Reinholdt A, Bendix J, Sauer SPA. The importance of relativistic effects for carbon as an NMR reporter nucleus in carbide bridged [RuCPt]-complexes. Organometallics. 2021 May 24;40(10):1443-1453. https://doi.org/10.1021/acs.organomet.1c00079

Author

Glent-Madsen, Iben ; Reinholdt, Anders ; Bendix, Jesper ; Sauer, Stephan P. A. / The importance of relativistic effects for carbon as an NMR reporter nucleus in carbide bridged [RuCPt]-complexes. In: Organometallics. 2021 ; Vol. 40, No. 10. pp. 1443-1453.

Bibtex

@article{691ba9eb742b4ca8a2f9424adef9cc12,
title = "The importance of relativistic effects for carbon as an NMR reporter nucleus in carbide bridged [RuCPt]-complexes",
abstract = "Carbide-bridged ruthenium platinum complexes of the general formula trans-(Cy3P)2Cl2Ru≡C-PtCl2-L show a remarkable ability to probe the ligand donor strength of the ligand L. An experimentally observed linear correlation between carbide chemical shifts (shielding) and the platinum-carbide (Pt-C) coupling constants in the complexes is investigated computationally to understand the origin of this trend. The shielding and coupling constants are computed at the two-component/spin-orbit ZORA-DFT level. The calculated values are in good agreement with the experimental values and reproduce the observed linear variation, even though relativistic effects are large and significant, especially for the Pt-C coupling constants. Analysis of the contributions to the shielding constants indicates that σ(C) is relatively more influenced by relativistic effects than σ(Ru). The variation in σ(C) originates from the spin-orbit coupling contribution, whereas the Fermi contact term is responsible for the changes in J(Pt-C) as the trans-influence of L changes. The linear correlation between parameters is therefore an illustration of the similarity of the mechanism underlying both contributions. The results are further analyzed by decomposition into contributions from natural localized molecular orbitals (NLMOs). The character of the individual NLMOs changes little along the series of complexes, and the variation in σ(C) is to equal amounts due to contributions from NLMOs associated with the Ru≡C and with the Pt-C bonds. The variation in the Pt-C coupling, on the other hand, is mainly due to variation in the contributions from NLMOs associated with only the Pt-C bond.",
keywords = "Faculty of Science, NMR, chemical shift, Spin-spin coupling constant, Chemical shielding, trans-effect, Carbide-complexes, ruthenium, platinum, relativistic effects, spin-orbit coupling, Density functional theory, ZORA",
author = "Iben Glent-Madsen and Anders Reinholdt and Jesper Bendix and Sauer, {Stephan P. A.}",
year = "2021",
month = may,
day = "24",
doi = "10.1021/acs.organomet.1c00079",
language = "English",
volume = "40",
pages = "1443--1453",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "10",

}

RIS

TY - JOUR

T1 - The importance of relativistic effects for carbon as an NMR reporter nucleus in carbide bridged [RuCPt]-complexes

AU - Glent-Madsen, Iben

AU - Reinholdt, Anders

AU - Bendix, Jesper

AU - Sauer, Stephan P. A.

PY - 2021/5/24

Y1 - 2021/5/24

N2 - Carbide-bridged ruthenium platinum complexes of the general formula trans-(Cy3P)2Cl2Ru≡C-PtCl2-L show a remarkable ability to probe the ligand donor strength of the ligand L. An experimentally observed linear correlation between carbide chemical shifts (shielding) and the platinum-carbide (Pt-C) coupling constants in the complexes is investigated computationally to understand the origin of this trend. The shielding and coupling constants are computed at the two-component/spin-orbit ZORA-DFT level. The calculated values are in good agreement with the experimental values and reproduce the observed linear variation, even though relativistic effects are large and significant, especially for the Pt-C coupling constants. Analysis of the contributions to the shielding constants indicates that σ(C) is relatively more influenced by relativistic effects than σ(Ru). The variation in σ(C) originates from the spin-orbit coupling contribution, whereas the Fermi contact term is responsible for the changes in J(Pt-C) as the trans-influence of L changes. The linear correlation between parameters is therefore an illustration of the similarity of the mechanism underlying both contributions. The results are further analyzed by decomposition into contributions from natural localized molecular orbitals (NLMOs). The character of the individual NLMOs changes little along the series of complexes, and the variation in σ(C) is to equal amounts due to contributions from NLMOs associated with the Ru≡C and with the Pt-C bonds. The variation in the Pt-C coupling, on the other hand, is mainly due to variation in the contributions from NLMOs associated with only the Pt-C bond.

AB - Carbide-bridged ruthenium platinum complexes of the general formula trans-(Cy3P)2Cl2Ru≡C-PtCl2-L show a remarkable ability to probe the ligand donor strength of the ligand L. An experimentally observed linear correlation between carbide chemical shifts (shielding) and the platinum-carbide (Pt-C) coupling constants in the complexes is investigated computationally to understand the origin of this trend. The shielding and coupling constants are computed at the two-component/spin-orbit ZORA-DFT level. The calculated values are in good agreement with the experimental values and reproduce the observed linear variation, even though relativistic effects are large and significant, especially for the Pt-C coupling constants. Analysis of the contributions to the shielding constants indicates that σ(C) is relatively more influenced by relativistic effects than σ(Ru). The variation in σ(C) originates from the spin-orbit coupling contribution, whereas the Fermi contact term is responsible for the changes in J(Pt-C) as the trans-influence of L changes. The linear correlation between parameters is therefore an illustration of the similarity of the mechanism underlying both contributions. The results are further analyzed by decomposition into contributions from natural localized molecular orbitals (NLMOs). The character of the individual NLMOs changes little along the series of complexes, and the variation in σ(C) is to equal amounts due to contributions from NLMOs associated with the Ru≡C and with the Pt-C bonds. The variation in the Pt-C coupling, on the other hand, is mainly due to variation in the contributions from NLMOs associated with only the Pt-C bond.

KW - Faculty of Science

KW - NMR

KW - chemical shift

KW - Spin-spin coupling constant

KW - Chemical shielding

KW - trans-effect

KW - Carbide-complexes

KW - ruthenium

KW - platinum

KW - relativistic effects

KW - spin-orbit coupling

KW - Density functional theory

KW - ZORA

U2 - 10.1021/acs.organomet.1c00079

DO - 10.1021/acs.organomet.1c00079

M3 - Journal article

VL - 40

SP - 1443

EP - 1453

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 10

ER -

ID: 260603572