title: 2H NMR calculations on polynuclear transition metal complexes: on the influence of local symmetry and other factors.
abstract: It is now well-known that (2)H 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 D(4)Ru(4)(CO)(12), D(2)Ru(6)(CO)(18) and other related compounds [Gutmann et al., J. Am. Chem. Soc., 2010, 132, 11759], which are model compounds for edge-bridging (μ-H) and face-capping (μ(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, η(2)-D(2), μ-D, μ(3)-D as well as μ(4)-D and μ(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.
authors: Université de Toulouse, INSA, UPS, CNRS, LPCNO, 135 avenue de Rangueil, F-31077 Toulouse, France.
authors: Iker
authors: I
authors: del Rosal
authors: Torsten
authors: T
authors: Gutmann
authors: Bernadeta
authors: B
authors: Walaszek
authors: Iann C
authors: IC
authors: Gerber
authors: Bruno
authors: B
authors: Chaudret
authors: Hans-Heinrich
authors: HH
authors: Limbach
authors: Gerd
authors: G
authors: Buntkowsky
authors: Romuald
authors: R
authors: Poteau