Relativistic effects in NMR properties of L[RuCPt] complexes: ZORA versus four-component calculations

Iben Glent-Madsen; Jesper Bendix; Stephan P. A. Sauer

Relativistic effects in NMR properties of ^L[RuCPt] complexes: ZORA versus four-component calculations

Iben Glent-Madsen^*, Jesper Bendix, Stephan P. A. Sauer

^*Corresponding author af dette arbejde

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Abstract

Ruthenium-carbide complexes are of great interest due to the possible bond formation and breakage to the carbide, e.g. as a catalyst in the Fischer-Tropsch synthesis [1,2] or the natural nitrogen fixation at nitrogenase cofactors [3,4]. Hetero-metallic carbide-bridged complexes (Cy3P)2Cl2Ru≡C-PtCl2L, ^L[RuCPt], with various ligands L have been synthesized and characterized using NMR spectroscopy by Reinholdt and Bendix [5]. The ligands L differ in their electron donating ability and thereby their trans-influence propensity in relation to the {Ru≡C} unit in ^L[RuCPt].
The experimental NMR studies are supplemented with theoretical studies using two relativistic methods: a four-component fully relativistic approach using the ReSpect program [6] and the Zeroth-order regular approximation (ZORA) [7] two-component method as implemented in the ADF program [8]. NMR chemical shifts of ruthenium, platinum and the carbide in various ^L[RuCPt] complexes were calculated at the DFT level using the PBE0 exchange-correlation functional. Basis set dependency, relativistic effects and contributions when calculating NMR properties, and a comparison of calculated results with experimental chemical shifts will be presented with focus on the results from two ^L[RuCPt] complexes.

Originalsprog	Engelsk
Publikationsdato	19 aug. 2019
Status	Udgivet - 19 aug. 2019
Begivenhed	Grand Challenges for Theoretical Chemistry: A conference on the occasion of Prof. Dr. Scient. Kurt V. Mikkelsen's 60th birthday - Konventum, Helsingør, Danmark Varighed: 19 aug. 2019 → 21 aug. 2019 http://folk.ntnu.no/aastrand/GCTC_2019/

Konference

Konference	Grand Challenges for Theoretical Chemistry
Lokation	Konventum
Land/Område	Danmark
By	Helsingør
Periode	19/08/2019 → 21/08/2019
Internetadresse	http://folk.ntnu.no/aastrand/GCTC_2019/

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iben_glent-madsenAndet version, 268 KB

Citationsformater

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title = "Relativistic effects in NMR properties of L[RuCPt] complexes: ZORA versus four-component calculations",

abstract = "Ruthenium-carbide complexes are of great interest due to the possible bond formation and breakage to the carbide, e.g. as a catalyst in the Fischer-Tropsch synthesis [1,2] or the natural nitrogen fixation at nitrogenase cofactors [3,4]. Hetero-metallic carbide-bridged complexes (Cy3P)2Cl2Ru≡C-PtCl2L, L[RuCPt], with various ligands L have been synthesized and characterized using NMR spectroscopy by Reinholdt and Bendix [5]. The ligands L differ in their electron donating ability and thereby their trans-influence propensity in relation to the {Ru≡C} unit in L[RuCPt].The experimental NMR studies are supplemented with theoretical studies using two relativistic methods: a four-component fully relativistic approach using the ReSpect program [6] and the Zeroth-order regular approximation (ZORA) [7] two-component method as implemented in the ADF program [8]. NMR chemical shifts of ruthenium, platinum and the carbide in various L[RuCPt] complexes were calculated at the DFT level using the PBE0 exchange-correlation functional. Basis set dependency, relativistic effects and contributions when calculating NMR properties, and a comparison of calculated results with experimental chemical shifts will be presented with focus on the results from two L[RuCPt] complexes.",

author = "Iben Glent-Madsen and Jesper Bendix and Sauer, {Stephan P. A.}",

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language = "English",

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AU - Glent-Madsen, Iben

AU - Bendix, Jesper

AU - Sauer, Stephan P. A.

PY - 2019/8/19

Y1 - 2019/8/19

N2 - Ruthenium-carbide complexes are of great interest due to the possible bond formation and breakage to the carbide, e.g. as a catalyst in the Fischer-Tropsch synthesis [1,2] or the natural nitrogen fixation at nitrogenase cofactors [3,4]. Hetero-metallic carbide-bridged complexes (Cy3P)2Cl2Ru≡C-PtCl2L, L[RuCPt], with various ligands L have been synthesized and characterized using NMR spectroscopy by Reinholdt and Bendix [5]. The ligands L differ in their electron donating ability and thereby their trans-influence propensity in relation to the {Ru≡C} unit in L[RuCPt].The experimental NMR studies are supplemented with theoretical studies using two relativistic methods: a four-component fully relativistic approach using the ReSpect program [6] and the Zeroth-order regular approximation (ZORA) [7] two-component method as implemented in the ADF program [8]. NMR chemical shifts of ruthenium, platinum and the carbide in various L[RuCPt] complexes were calculated at the DFT level using the PBE0 exchange-correlation functional. Basis set dependency, relativistic effects and contributions when calculating NMR properties, and a comparison of calculated results with experimental chemical shifts will be presented with focus on the results from two L[RuCPt] complexes.

AB - Ruthenium-carbide complexes are of great interest due to the possible bond formation and breakage to the carbide, e.g. as a catalyst in the Fischer-Tropsch synthesis [1,2] or the natural nitrogen fixation at nitrogenase cofactors [3,4]. Hetero-metallic carbide-bridged complexes (Cy3P)2Cl2Ru≡C-PtCl2L, L[RuCPt], with various ligands L have been synthesized and characterized using NMR spectroscopy by Reinholdt and Bendix [5]. The ligands L differ in their electron donating ability and thereby their trans-influence propensity in relation to the {Ru≡C} unit in L[RuCPt].The experimental NMR studies are supplemented with theoretical studies using two relativistic methods: a four-component fully relativistic approach using the ReSpect program [6] and the Zeroth-order regular approximation (ZORA) [7] two-component method as implemented in the ADF program [8]. NMR chemical shifts of ruthenium, platinum and the carbide in various L[RuCPt] complexes were calculated at the DFT level using the PBE0 exchange-correlation functional. Basis set dependency, relativistic effects and contributions when calculating NMR properties, and a comparison of calculated results with experimental chemical shifts will be presented with focus on the results from two L[RuCPt] complexes.

M3 - Poster

T2 - Grand Challenges for Theoretical Chemistry

Y2 - 19 August 2019 through 21 August 2019

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