31P Chemical Shifts in Ru(II) Phosphine Complexes. A Computational Study of the Influence of the Coordination Sphere.
31P Chemical Shifts in Ru(II) Phosphine Complexes. A Computational Study of the Influence of the Coordination Sphere.
复制标题
Ru(II) 膦配合物中的 31P 化学位移。
作者：
C. Raynaud;Eliott Norbert;B. James;O. Eisenstein
NMR 化学位移通过反映全局和局部电子结构，成为最通用的化学结构标记，并且对化学物质内的任何变化非常敏感。在这项工作中，通过使用配位二齿 PA-N 配体 (PA-N = 邻二苯基膦-N,N'-二甲基苯胺）。 RuCl2(PA-N)(PR3)(L)（R = 苯基、对甲苯基或 p-FC6H4）中 PA 的化学位移随着 Ru-PA 键距的减小而增加，这一观察结果并未合理化。这项工作使用密度泛函理论 (DFT) 计算，相当好地再现了观察到的这些配合物的 31P 化学位移，以及随着 L 变化，位移与 Ru-PA 键距之间的相关性。通过使用基于自然键合轨道（NBO）方法的自然化学位移（NCS）分析提出了对这种相关性的解释。对化学位移张量主成分的分析表明，L 的 σ 供给特性如何对磷化氢化学位移产生特别大的影响。
The NMR chemical shift has been the most versatile marker of chemical structures, by reflecting global and local electronic structures, and is very sensitive to any change within the chemical species. In this work, Ru(II) complexes with the same five ligands and a variable sixth ligand L (none, H2O, H2S, CH3SH, H2, N2, N2O, NO+, C═CHPh, and CO) are studied by using as the NMR reporter the phosphorus PA of a coordinated bidentate PA-N ligand (PA-N = o-diphenylphosphino-N,N'-dimethylaniline). The chemical shift of PA in RuCl2(PA-N)(PR3)(L) (R = phenyl, p-tolyl, or p-FC6H4) was shown to increase as the Ru-PA bond distance decreases, an observation that was not rationalized. This work, using density functional theory (DFT) calculations, reproduces reasonably well the observed 31P chemical shifts for these complexes and the correlation between the shifts and the Ru-PA bond distance as L varies. An interpretation of this correlation is proposed by using a natural chemical shift (NCS) analysis based on the natural bonding orbital (NBO) method. This analysis of the principal components of the chemical shift tensors shows how the σ-donating properties of L have a particularly high influence on the phosphine chemical shifts.
化学位移张量：分子结构问题的理论与应用。
DOI：
10.1016/j.pnmrs.2010.10.003
发表时间：
2011-05
影响因子：
6.1
作者：
Facelli, Julio C.
通讯作者：
Facelli, Julio C.
通过量子化学研究破译无序系统的核磁共振指纹。
DOI：
10.1021/jp9001324
发表时间：
2009
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
Ling,Yan;Zhang,Yong
通讯作者：
Zhang,Yong