Dynamic and Static Behaviors of N-Z-N σ(3c-4e)(Z=S, Se, and Te) Interactions : Atoms-in-Molecules Dual Functional Analysis with High-Resolution X-ray Diffraction Determination of Electron Densities for 2-(2-Pyridylimino)-2H-1,2,4-thiadiazolo[2,3-α]pyridin
Dynamic and Static Behaviors of N-Z-N σ(3c-4e)(Z=S, Se, and Te) Interactions : Atoms-in-Molecules Dual Functional Analysis with High-Resolution X-ray Diffraction Determination of Electron Densities for 2-(2-Pyridylimino)-2H-1,2,4-thiadiazolo[2,3-α]pyridin
复制标题
N-Z-N σ(3c-4e)(Z=S、Se 和 Te) 相互作用的动态和静态行为：分子中原子双功能分析和高分辨率 X 射线衍射测定 2-(2-) 的电子密度吡啶亚氨基)-2H-1,2,4-噻二唑并[2,3-α]吡啶
DOI：
10.1021/jp2044898
复制
发表时间：
2011
期刊：
影响因子：
--
通讯作者：
S.J.Coles
中科院分区：
文献类型：
--
作者：
W.Nakanishi;S.Hayashi;M.B.Pitak;M.B.Hursthouse;S.J.Coles
2-(2-pyridylimino)-2H-1，2，4-thiadiazolo[2，3-a]pyridine(NSN)的结构表明，该分子具有具有线性N···S···N键的平面几何结构，形成形式C2v对称性的四环结构。为了阐明NsNσ(3c-4e)键的性质，以及相关的NSen和NTEn，应用原子在分子中的双泛函分析对完全优化和微扰结构进行了动态和静态行为的研究。通过计算对结构进行了优化，保持了C2v对称性。所有的键临界点都被检测到，并显示在支持形成σ(3c-4e)的N···Z···N部分的两侧。证实了N···S···N的共价性接近于Me2S+-∗-Cl或Me2Se+-∗-Br，而N···Se···N和N···Te···N分别具有接近Me2S(-∗-Cl)2(TBP)和Me2Se-∗-Br2(MC)的CT加合物的(规则)CS性质。在NSN上进行了高分辨电荷密度的实验测定，完全支持了理论结果。在N···S···N、N···Se···N和N···Te···N的类似的嘧啶类化合物中也得到了非常相似的结果。AIM双泛函分析被实验的高分辨电荷密度证实是解释这些相互作用的一种很好的方法。
The structure of 2-(2-pyridylimino)-2H-1,2,4-thiadiazolo[2,3-a]pyridine (NSN) indicates that the molecule has a planar geometry with a linear N···S···N linkage, creating a tetracyclic structure of the formalC2vsymmetry. To clarify the nature of the NSN σ(3c–4e) bonding, together with the related NSeN and NTeN, the dynamic and static behaviors are investigated by applying atoms-in-molecules (AIM) dual functional analysis to both the fully optimized and perturbed structures. The structures were optimized computationally, retainingC2vsymmetry. All bond critical points are detected as expected and exhibited on both sides of the N···Z···N moiety which supports the formation of NZN σ(3c–4e). It is confirmed that N···S···N is of the covalent nature close to Me2S+-∗-Cl or Me2Se+-∗-Br, whereas N···Se···N and N···Te···N have the (regular) CS nature close to the CT adducts of Me2S(-∗-Cl)2(TBP) and Me2Se-∗-Br2(MC), respectively. An experimental high-resolution charge density determination has been performed on NSN, which thoroughly supports the theoretical results. Very similar results are obtained in the analogous pyrimidyl derivatives for N···S···N, N···Se···N, and N···Te···N. AIM dual functional analysis, as validated by experimental high-resolution charge densities, is thus confirmed to be an excellent method to elucidate the nature of these interactions.