Evaluation of (95)Mo Nuclear Shielding and Chemical Shift of [Mo6X14](2-) Clusters in the Liquid Phase.
Evaluation of (95)Mo Nuclear Shielding and Chemical Shift of [Mo6X14](2-) Clusters in the Liquid Phase.
复制标题
(95)Mo 核屏蔽和[Mo6X14](2-)团簇在液相中的化学位移的评估。
DOI：
10.1021/acs.inorgchem.5b00396
复制
发表时间：
2015
影响因子：
4.6
通讯作者：
Nguyen TT
中科院分区：
文献类型：
--
作者：
Nguyen TT
[Mo6X14]2–octahedral molybdenum clusters are the main building blocks of a large range of materials. Although95Mo nuclear magnetic resonance was proposed to be a powerful tool to characterize their structural and dynamical properties in solution, these measurements have never been complemented by theoretical studies which can limit their interpretation for complex systems. In this Article, we use quantum chemical calculations to evaluate the95Mo chemical shift of three clusters: [Mo6Cl14]2–, [Mo6Br14]2–, and [Mo6I14]2–. In particular, we test various computational parameters influencing the quality of the results: size of the basis set, treatment of relativistic and solvent effects. Furthermore, to provide quantum chemical calculations that are directly comparable with experimental data, we evaluate for the first time the95Mo nuclear magnetic shielding of the experimental reference, namely, MoO42–in aqueous solution. This is achieved by combining ab initio molecular dynamics simulations with a periodic approach to evaluate the95Mo nuclear shieldings. The results demonstrate that, despite the difficulty to obtain accurate95Mo chemical shifts, relative values for a cluster series can be fairly well-reproduced by DFT calculations. We also show that performing an explicit solvent treatment for the reference compound improves by ∼50 ppm the agreement between theory and experiment. Finally, the standard deviation of ∼70 ppm that we calculate for the95Mo nuclear shielding of the reference provides an estimation of the accuracy we can achieve for the calculation of the95Mo chemical shifts using a static approach. These results demonstrate the growing ability of quantum chemical calculations to complement and interpret complex experimental measurements.
登录
查看更多内容
19F-NMR-光谱学和统计研究 [(Mo6I niCl 8−ni)F 6a]2−, n = 0–7, und Darstellung von (TBA)2[(Mo6I 8i)F 6a]
DOI：
--
发表时间：
1993
期刊：
影响因子：
--
作者：
P. Brückner;G. Peters;W. Preetz
通讯作者：
W. Preetz
95Mo 固态核磁共振波谱和量子模拟：钼簇材料研究的协同工具。
影响因子：
4.6
作者：
J. Cuny;S. Cordier;C. Perrin;C. Pickard;L. Delevoye;J. Trébosc;Z. Gan;L. le Pollès;R. Gautier
通讯作者：
R. Gautier
Cu2Mo6X14 中的三角平面 CuX3-Gruppen，X = Cl、Br、I
DOI：
--
发表时间：
1996
期刊：
影响因子：
--
作者：
A. Peppenhorst;H. Keller
通讯作者：
H. Keller
溶剂对配合物 [(NC)5Pt--Tl(CN)n]n- (n=0-3) 和 [(NC)5Pt--Tl--Pt(CN) 的 195Pt 和 205Tl NMR 化学位移的影响
影响因子：
--
作者：
J. Autschbach;B. le Guennic
通讯作者：
B. le Guennic
铂铊键配合物的NMR性质：相对论密度泛函理论结果分析
DOI：
--
发表时间：
2004
期刊：
Magnetic resonance in chemistry : MRC
影响因子：
--
作者：
B. le Guennic;Kazuko Matsumoto;J. Autschbach
通讯作者：
J. Autschbach