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C(sp3) atoms as tetrel bond donors: A crystallographic survey
Coordination Chemistry Reviews ( IF 20.6 ) Pub Date : 2020-03-10 , DOI: 10.1016/j.ccr.2020.213265
Andrea Daolio , Patrick Scilabra , Giancarlo Terraneo , Giuseppe Resnati

The σ-hole and π-hole interactions allow for a systematic understanding of some features of the attractive interactions involving elements of groups 13–18 of the periodic table and of some other groups. Areas of depleted electron density, where the electrostatic potential can be positive, exist on these atoms and these areas can form attractive interactions with electron rich sites (nucleophiles). When the electrophilic atom belongs to groups 14, 15, 16, or 17, the resulting interactions are named tetrel, pnictogen, chalcogen, and halogen bond, respectively. Here we discuss the tetrel bonds (TtBs) formed in crystalline solids on interaction of sp3 hybridized carbon atoms with lone pair possessing atoms and anions. A mapping of the specific short contacts formed in the solid by C(sp3) atoms is realized by discussing selected structures from the Cambridge Structural Database. This mapping led to the identification of some functional groups particularly tailored to form TtBs which can affect or control the packing in crystalline solids. Specifically, it is shown that methyl and methylene groups bound to ammonium, pyridinium, and sulfonium residues can give rise to particularly short and directional TtBs. Topologically, the formed adducts can exist as discrete species or one, two, or three dimensional networks. Fluorine atoms and perfluorinated residues as well as nitro and cyano substituents can also lead to the formation of TtBs which can control molecular conformation and packing in the solid.



中文翻译:

C(sp 3)原子作为蝶形键的供体:晶体学调查

σ孔和π孔相互作用可以系统地理解涉及元素周期表第13-18组和某些其他组的有吸引力的相互作用的某些特征。在这些原子上存在静电势可以为正的耗尽电子密度的区域,这些区域可以与富电子位点(亲核试剂)形成有吸引力的相互作用。当亲电子原子属于第14、15、16或17个基团时,所得相互作用分别称为替特雷尔,光变原,硫属元素和卤素键。在这里,我们讨论了在sp 3杂化碳原子与具有原子和阴离子的孤对相互作用时在结晶固体中形成的锡铁键(TtBs)。C(sp 3在实体中形成的特定短触点的映射)原子是通过讨论剑桥结构数据库中的选定结构来实现的。该映射导致鉴定了一些特别为形成TtB而设计的官能团,这些官能团可以影响或控制结晶固体中的堆积。具体地,表明结合至铵,吡啶鎓和sulf残基的甲基和亚甲基可产生特别短且定向的TtB。在拓扑上,形成的加合物可以离散的物种或一维,二维或三维网络的形式存在。氟原子和全氟残基以及硝基和氰基取代基也会导致TtB的形成,从而可控制分子的构象和固体中的堆积。

更新日期:2020-03-10
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