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DFT (2)H quadrupolar coupling constants of ruthenium complexes: a good probe of the coordination of hydrides in conjuction with experiments

del Rosal, I. and Gutmann, T. and Maron, L. and Jolibois, F. and Chaudret, B. and Walaszek, B. and Limbach, H. H. and Poteau, R. and Buntkowsky, G. (2009):
DFT (2)H quadrupolar coupling constants of ruthenium complexes: a good probe of the coordination of hydrides in conjuction with experiments.
In: Physical Chemistry Chemical Physics, pp. 5657-5663, 11, (27), [Online-Edition: http://apps.webofknowledge.com/full_record.do?product=WOS&se...],
[Article]

Abstract

Transition metal (TM) hydrides are of great interest in chemistry because of their reactivity and their potential as catalysts for hydrogenation reactions. (2)H solid-state NMR can be used in order to get information about the local environment of hydrogen atoms, and more particularly the coordination mode of hydrides in such complexes. In this work we will show that it is possible to establish at the level of density functional theory (DFT) a viable methodological strategy that allows the determination of (2)H NMR parameters, namely the quadrupolar coupling constant (C(Q)) respectively the quadrupolar splitting (Delta nu(Q)) and the asymmetry parameter (eta(Q)). The reliability of the method (B3PW91-DFT) and basis set effects have been first evaluated for simple organic compounds (benzene and fluorene). A good correlation between experimental and theoretical values is systematically obtained if the large basis set cc-pVTZ is used for the computations. (2)H NMR properties of five mononuclear ruthenium complexes (namely Cp* RuD(3)(PPh(3)), Tp*RuD(THT)(2), Tp*RuD(D(2))(THT) and Tp*RuD(D(2))(2) and RuD(2)(D(2))(2)(PCy(3))(2)) which exhibit different ligands and hydrides involved in different coordination modes (terminal-H or eta(2)-H(2)), have been calculated and compared to previous experimental data. The results obtained are in excellent agreement with experiments. Although (2)H NMR spectra are not always easy to analyze, assistance by quantum chemistry calculations allows unambiguous assignment of the signals of such spectra. As far as experiments can be achieved at very low temperatures in order to avoid dynamic effects, this hybrid theoretical/experimental tool may give useful insights in the context of the characterization of ruthenium surfaces or nanoparticles with solid-state NMR.

Item Type: Article
Erschienen: 2009
Creators: del Rosal, I. and Gutmann, T. and Maron, L. and Jolibois, F. and Chaudret, B. and Walaszek, B. and Limbach, H. H. and Poteau, R. and Buntkowsky, G.
Title: DFT (2)H quadrupolar coupling constants of ruthenium complexes: a good probe of the coordination of hydrides in conjuction with experiments
Language: English
Abstract:

Transition metal (TM) hydrides are of great interest in chemistry because of their reactivity and their potential as catalysts for hydrogenation reactions. (2)H solid-state NMR can be used in order to get information about the local environment of hydrogen atoms, and more particularly the coordination mode of hydrides in such complexes. In this work we will show that it is possible to establish at the level of density functional theory (DFT) a viable methodological strategy that allows the determination of (2)H NMR parameters, namely the quadrupolar coupling constant (C(Q)) respectively the quadrupolar splitting (Delta nu(Q)) and the asymmetry parameter (eta(Q)). The reliability of the method (B3PW91-DFT) and basis set effects have been first evaluated for simple organic compounds (benzene and fluorene). A good correlation between experimental and theoretical values is systematically obtained if the large basis set cc-pVTZ is used for the computations. (2)H NMR properties of five mononuclear ruthenium complexes (namely Cp* RuD(3)(PPh(3)), Tp*RuD(THT)(2), Tp*RuD(D(2))(THT) and Tp*RuD(D(2))(2) and RuD(2)(D(2))(2)(PCy(3))(2)) which exhibit different ligands and hydrides involved in different coordination modes (terminal-H or eta(2)-H(2)), have been calculated and compared to previous experimental data. The results obtained are in excellent agreement with experiments. Although (2)H NMR spectra are not always easy to analyze, assistance by quantum chemistry calculations allows unambiguous assignment of the signals of such spectra. As far as experiments can be achieved at very low temperatures in order to avoid dynamic effects, this hybrid theoretical/experimental tool may give useful insights in the context of the characterization of ruthenium surfaces or nanoparticles with solid-state NMR.

Journal or Publication Title: Physical Chemistry Chemical Physics
Volume: 11
Number: 27
Uncontrolled Keywords: solid-state nmr transition-metal dihydrides generalized gradient approximation sterol-membrane interactions chemical-shifts basis-sets ab-initio catalysts c-13 spectroscopy
Divisions: 07 Department of Chemistry
07 Department of Chemistry > Physical Chemistry
Date Deposited: 27 Oct 2014 20:38
Official URL: http://apps.webofknowledge.com/full_record.do?product=WOS&se...
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467GW Times Cited:13 Cited References Count:51

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