Organisch-Chemisches Institut, Universität Heidelberg , Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany.
Institut für Organische Chemie, Universität Duisburg-Essen , Universitätsstraße 7, D-45117 Essen, Germany.
Chem Rev. 2018 Feb 28;118(4):2010-2041. doi: 10.1021/acs.chemrev.7b00449. Epub 2018 Feb 8.
This review considers noncovalent bonds between divalent chalcogen centers. In the first part we present X-ray data taken from the solid state structures of dimethyl- and diphenyl-dichalcogenides as well as oligoalkynes kept by alkyl-sulfur, -selenium, and -tellurium groups. Furthermore, we analyzed the solid state structures of medium sized (12-24 ring size) selenium coronands and medium to large rings with alkyne and alkene units between two chalcogen centers. The crystal structures of the cyclic structures revealed columnar stacks with close contacts between neighboring rings via noncovalent interactions between the chalcogen centers. To get larger space within the cavities, rings with diyne units between the chalcogen centers were used. These molecules showed channel-like structures in the solid state. The flexibility of the rings permits inclusion of guest molecules such as five-membered heterocycles and aromatic six-membered rings. In the second part we discuss the results of quantum chemical calculations. To treat properly the noncovalent bonding between chalcogens, we use diffuse augmented split valence basis sets in combination with electron correlation methods. Our model substances were 16 dimers consisting of two Me-X-Me (X = O, S, Se, Te) pairs and dimers of Me-X-Me/Me-X-CN (X = O, S, Se, Te) pairs. The calculations show the anticipated increase of the interaction energy from (Me-O-Me) (-2.15 kcal/mol) to (Me-O-Me/Me-Te-CN) (-6.59 kcal/mol). An analysis by the NBO method reveals that in the case of the chalcogen centers O and S the hydrogen bridges between the molecules dominate. However, in the case of Se and Te the major bonding between the pairs originates from dispersion forces between the chalcogen centers. It varies between -1.7 and -4.0 kcal/mol.
这篇综述考虑了二价硫属元素中心之间的非共价键。在第一部分，我们展示了从二甲基和二苯基二硫醚以及由烷基硫、硒和碲基团保持的寡炔的固态结构中获得的 X 射线数据。此外，我们分析了中等大小（12-24 环大小）硒冠状物和在两个硫属元素中心之间具有炔和烯烃单元的中到大环的固态结构。环状结构的晶体结构显示了柱状堆积，通过硫属元素中心之间的非共价相互作用，相邻环之间存在紧密接触。为了在空腔内获得更大的空间，使用了在硫属元素中心之间具有二炔单元的环。这些分子在固态下显示出通道状结构。环的柔韧性允许包括客分子，如五元杂环和芳香六元环。在第二部分，我们讨论了量子化学计算的结果。为了正确处理硫属元素之间的非共价键，我们使用了弥散增强分裂价基组结合电子相关方法。我们的模型物质是由两个 Me-X-Me（X = O、S、Se、Te）对和 Me-X-Me/Me-X-CN（X = O、S、Se、Te）对组成的 16 个二聚体。计算表明，相互作用能从（Me-O-Me）（-2.15 kcal/mol）增加到（Me-O-Me/Me-Te-CN）（-6.59 kcal/mol）。NBO 方法的分析表明，对于硫属元素中心 O 和 S，分子之间的氢键占主导地位。然而，对于 Se 和 Te，对分子之间的主要键合起源于硫属元素中心之间的色散力。它在-1.7 到-4.0 kcal/mol 之间变化。
