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首页> 外文期刊>Coordination chemistry reviews >Electron-rich two-, three- and four-center bonds between chalcogens - New prospects for old molecules
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Electron-rich two-, three- and four-center bonds between chalcogens - New prospects for old molecules

机译：硫族元素之间的富电子二，三和四中心键-旧分子的新前景

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摘要

The focus of this review is the nature of a third covalent bond between two divalent chalcogen centers. This bond is longer than a single bond and less than the van der Waals distance between two chalcogen atoms. Such a bond is only possible when electron density is withdrawn from the divalent chalcogens. For two sulfur centers this means S center dot center dot center dot S bond lengths between 2.3 angstrom and 3.1 angstrom. Our discussion is based on model systems, such as various trithiapentalene derivatives, 1,5-dithia-2,4,6,8-tetrazocine and related SN cage systems, the dimers of a 1,3-dithia-2,4,6-triazine radical, and systems adopting 2-center-3-electron and 4-center-6-electron bonds, respectively, between two or four sulfur centers. The leitmotiv of this review is that the loss of electron density at the divalent sulfides can lead to trivalent sulfur centers. This behavior is first rationalized qualitatively by simple MO models. The properties of the models are reproduced by high level quantum chemical methods. (C) 2017 Elsevier B.V. All rights reserved.
机译：这篇综述的重点是两个二价硫属元素中心之间的第三共价键的性质。该键比单键长，并且小于两个硫族元素原子之间的范德华距离。仅当从二价硫族元素撤出电子密度时，这种键才可能。对于两个硫中心，这意味着S中心点中心点中心点S点的键合长度在2.3埃和3.1埃之间。我们的讨论基于模型系统，例如各种三硫杂戊烯衍生物，1,5-二硫-2,4,6,8-四唑啉和相关的SN笼系统，1,3-二硫-2,4,6的二聚体-三嗪自由基，以及在两个或四个硫中心之间分别采用2中心3电子和4中心6电子键的系统。该评论的主旨是在二价硫化物处电子密度的损失会导致三价硫中心。首先通过简单的MO模型定性地合理化此行为。模型的特性通过高级量子化学方法重现。 （C）2017 Elsevier B.V.保留所有权利。

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