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H-2 NMR calculations on polynuclear transition metal complexes: on the influence of local symmetry and other factors

del Rosal, I. and Gutmann, T. and Walaszek, B. and Gerber, I. C. and Chaudret, B. and Limbach, H. H. and Buntkowsky, G. and Poteau, R. :
H-2 NMR calculations on polynuclear transition metal complexes: on the influence of local symmetry and other factors.
[Online-Edition: <Go to ISI>://WOS:000296871500022]
In: Physical Chemistry Chemical Physics, 13 (45) pp. 20199-20207.
[Article] , (2011)

Official URL: <Go to ISI>://WOS:000296871500022

Abstract

It is now well-known that H-2 solid-state NMR techniques can bring a better understanding of the interaction of deuterium with metal atoms in organometallic mononuclear complexes, clusters or nanoparticles. In that context, we have recently obtained experimental quadrupolar coupling constants and asymmetry parameters characteristic of deuterium atoms involved in various bonding situations in ruthenium clusters, namely D4Ru4(CO)(12), D2Ru6(CO)(18) and other related compounds Gutmann et al., J. Am. Chem. Soc., 2010, 132, 11759, which are model compounds for edge-bridging (mu-H) and face-capping (mu(3)-H) coordination types on ruthenium surfaces. The present work is in line with density functional theory (DFT) calculations of the electric field gradient (EFG) tensors in deuterated organometallic ruthenium complexes. The comparison of quadrupolar coupling constants shows an excellent agreement between calculated and observed values. This confirms that DFT is a method of choice for the analysis of deuterium NMR spectra. Such calculations are achieved on a large number of ruthenium clusters in order to obtain quadrupolar coupling constants characteristic of a given coordination type: terminal-D, eta(2)-D-2, mu-D, mu(3)-D as well as mu(4)-D and mu(6)-D (i.e. interstitial deuterides). Given the dependence of such NMR parameters mainly on local symmetry, these results are expected to remain valid for large assemblies of ruthenium atoms, such as organometallic ruthenium nanoparticles.

Item Type: Article
Erschienen: 2011
Creators: del Rosal, I. and Gutmann, T. and Walaszek, B. and Gerber, I. C. and Chaudret, B. and Limbach, H. H. and Buntkowsky, G. and Poteau, R.
Title: H-2 NMR calculations on polynuclear transition metal complexes: on the influence of local symmetry and other factors
Language: German
Abstract:

It is now well-known that H-2 solid-state NMR techniques can bring a better understanding of the interaction of deuterium with metal atoms in organometallic mononuclear complexes, clusters or nanoparticles. In that context, we have recently obtained experimental quadrupolar coupling constants and asymmetry parameters characteristic of deuterium atoms involved in various bonding situations in ruthenium clusters, namely D4Ru4(CO)(12), D2Ru6(CO)(18) and other related compounds Gutmann et al., J. Am. Chem. Soc., 2010, 132, 11759, which are model compounds for edge-bridging (mu-H) and face-capping (mu(3)-H) coordination types on ruthenium surfaces. The present work is in line with density functional theory (DFT) calculations of the electric field gradient (EFG) tensors in deuterated organometallic ruthenium complexes. The comparison of quadrupolar coupling constants shows an excellent agreement between calculated and observed values. This confirms that DFT is a method of choice for the analysis of deuterium NMR spectra. Such calculations are achieved on a large number of ruthenium clusters in order to obtain quadrupolar coupling constants characteristic of a given coordination type: terminal-D, eta(2)-D-2, mu-D, mu(3)-D as well as mu(4)-D and mu(6)-D (i.e. interstitial deuterides). Given the dependence of such NMR parameters mainly on local symmetry, these results are expected to remain valid for large assemblies of ruthenium atoms, such as organometallic ruthenium nanoparticles.

Journal or Publication Title: Physical Chemistry Chemical Physics
Volume: 13
Number: 45
Uncontrolled Keywords: solid-state nmr hydrogen adsorption coupling-constants dft calculations chemical-shifts nanoparticles surface parameters clusters spectroscopy
Divisions: 07 Fachbereich Chemie > Physical Chemistry
07 Fachbereich Chemie
Date Deposited: 27 Oct 2014 20:38
Official URL: <Go to ISI>://WOS:000296871500022
Additional Information:

846BF Times Cited:7 Cited References Count:39

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