Université de Toulouse, INSA, UPS, CNRS, LPCNO, 135 avenue de Rangueil, F-31077 Toulouse, France.
Phys Chem Chem Phys. 2011 Dec 7;13(45):20199-207. doi: 10.1039/c1cp22081k. Epub 2011 Oct 12.
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.
现在众所周知，（2）H 固态 NMR 技术可以更好地了解氘与有机金属单核配合物、团簇或纳米粒子中金属原子的相互作用。在这种情况下，我们最近获得了实验四极偶合常数和各向异性参数，这些参数与在各种键合情况下的氘原子有关，即在 Ru4(CO)12、D2Ru6(CO)18 和其他相关化合物[Gutmann 等人，J. Am. Chem. Soc.，2010，132，11759]中涉及的 Ru 团簇，这些都是 Ru 表面边缘桥接（μ-H）和面封端（μ(3)-H）配位类型的模型化合物。本工作符合含氘有机金属 Ru 配合物的电场梯度（EFG）张量密度泛函理论（DFT）计算。四极偶合常数的比较表明，计算值与观测值之间有极好的一致性。这证实了 DFT 是分析氘 NMR 谱的首选方法。对大量 Ru 团簇进行了这样的计算，以获得具有给定配位类型特征的四极偶合常数：端-D、η(2)-D2、μ-D、μ(3)-D 以及 μ(4)-D 和 μ(6)-D（即间隙氘化物）。鉴于这些 NMR 参数主要依赖于局部对称性，因此这些结果有望在 Ru 原子的大组装体中保持有效，例如有机金属 Ru 纳米粒子。
