Computational Chemistry Group, Department of Chemistry, University of Mauritius, Reduit, Mauritius.
J Mol Model. 2013 Jul;19(7):2739-46. doi: 10.1007/s00894-012-1571-4. Epub 2012 Sep 12.
It is well-established that many covalently-bonded atoms of Groups IV-VII have directionally-specific regions of positive electrostatic potential (σ-holes) through which they can interact with negative sites. In the case of Group VII, this is called "halogen bonding." We have studied two series of molecules: the F3MX and, for comparison, the H3MX (M = C, Si and Ge; X = F, Cl, Br and I). Our objective was to determine how the interplay between M and X in each molecule affects the σ-holes of both, and consequently their interactions with the nitrogen lone pair of HCN. We find that the relative electronegativities of M and X are not sufficient to explain their effects upon each other's σ-holes; consideration of charge capacity/polarizability (and perhaps other factors) also appears to be necessary. However the results do support the description of normal σ-hole interactions as being largely electrostatically-driven.
人们已经充分认识到，第 IV-VII 族的许多共价键原子都具有带正静电势的方向性特定区域（σ 空穴），可以通过这些区域与负电荷点相互作用。对于第 VII 族，这种相互作用被称为“卤键”。我们研究了两类分子：F3MX 和，作为比较，H3MX（M = C、Si 和 Ge；X = F、Cl、Br 和 I）。我们的目的是确定每个分子中 M 和 X 之间的相互作用如何影响两者的 σ 空穴，进而影响它们与 HCN 的氮孤对的相互作用。我们发现，M 和 X 的相对电负性不足以解释它们对彼此的 σ 空穴的影响；考虑电荷容量/极化率（也许还有其他因素）似乎也是必要的。然而，这些结果确实支持将正常的 σ 空穴相互作用主要描述为静电驱动。
