Solid-state 13C NMR and quantum chemical investigation of metal diene complexes.
Solid-state 13C NMR and quantum chemical investigation of metal diene complexes.
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金属二烯配合物的固态 13C NMR 和量子化学研究。
DOI：
10.1002/mrc.1981
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发表时间：
2007
期刊：
影响因子：
--
通讯作者：
Ernst,RichardD
中科院分区：
文献类型：
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作者：
Ma,Zhiru;Facelli,JulioC;Pugmire,RonaldJ;Dunn,BrianC;Turpin,GregoryC;Eyring,EdwardM;Ernst,RichardD
本文给出了几种金属双烯络合物中烯烃~(13)C化学位移张量主值的新测量和计算。实验值和计算结果表明，相对于母体烯烃化合物的值有高达70ppm的位移。这些位移是高度各向异性的，在张量的屏蔽较少的主分量中观察到最大的位移，在最屏蔽的主分量中观察到最小的位移。在乙烯和其他烯烃化合物中，张量的主成分的取向在10°内保持在它们的方向上。用Giao方法和LanDZ赝势基组计算的结果与实验符合得很好，并为双环[2.2.1]-2，5-二烯(BCHD)二氯钚(II)聚合物中氯桥结构的存在提供了确切的证据。版权所有©2007 John Wiley&Sons，Ltd.
This paper presents novel measurements and calculations of the olefinic13C chemical shift tensor principal values in several metal diene complexes. The experimental values and the calculations show shifts as large as 70 ppm with respect to the values in the parent olefinic compounds. These shifts are highly anisotropic, with the largest ones observed in the less shielded principal components and the smallest ones in the most shielded principal components of the tensor. The orientations of the principal components of the tensors remain, within 10°, at their directions in ethylene and other olefinic compounds. The calculations, performed using the GIAO method and the LanDZ pseudopotential basis set, show good agreement with the experiments, and were used to establish definite evidence for the existence of a Cl‐bridge structure in the bicyclo[2.2.1]hepta‐2,5‐diene (BCHD)dichlororuthenium(II) polymer. Copyright © 2007 John Wiley & Sons, Ltd.