Structure and Bonding in a Diamond-Shaped Tin Cluster Possessing a cyclo-Sn4 Core.,Chemistry - A European Journal

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Structure and Bonding in a Diamond-Shaped Tin Cluster Possessing a cyclo-Sn4 Core.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-05-08 , DOI: 10.1002/chem.202000969
Rex C Handford ₁ , T Alex Wheeler ₁ , T Don Tilley ₁

Affiliation

A tetrameric cluster composed entirely of (aryl)Sn units, [DMPSn]4 (DMP=2,6-dimesitylphenyl), has been prepared by reduction of [DMPSnCl]2 with a variety of reductants. This cluster was characterized in solution by multinuclear NMR spectroscopies, as well as in the solid-state by single crystal X-ray diffraction analysis. This species is stereochemically nonrigid in solution and possesses a cyclo-Sn4 core whose DMP substituents are equivalent at higher temperatures. The solid-state molecular structure is remarkably unsymmetrical and possesses a nearly planar cyclo-Sn4 core. The DMP substituents are arranged such that three are approximately coplanar, while one is nearly perpendicular to the cyclo-Sn4 core. Density functional theory calculations for a [PhSn]4 model system show that this distorted geometry about the cyclo-Sn4 core maximizes σ-bonding between the Sn centers in a manner reminiscent of trans-bent bonding in the heavy group 14 analogues of alkenes and alkynes.

中文翻译：

具有环Sn4核的菱形锡簇中的结构和键合。

通过用各种还原剂还原[DMPSnCl] 2，已经制备了完全由（芳基）Sn单元[DMPSn] 4（DMP = 2,6-二甲硅烷基苯基）组成的四聚体簇。该簇在溶液中通过多核NMR光谱表征，在固态中通过单晶X射线衍射分析表征。该物种在溶液中在立体化学上是非刚性的，并具有一个环Sn4核，其DMP取代基在较高温度下是等效的。固态分子结构显着不对称，并具有接近平面的环Sn4核。DMP取代基的排列应使三个近似共面，而一个则几乎垂直于环Sn4核。

更新日期：2020-03-26

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