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The term “σ-hole” was introduced by Clark et al to describe the regions of positive electrostatic potential that are present on the outer surfaces of many covalentlybonded halogens

σ-Holes, π-holes and electrostatically-driven interactions

Journal of Molecular Modeling, no. 2 (2012): 541-548

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摘要

A positive π-hole is a region of positive electrostatic potential that is perpendicular to a portion of a molecular framework. It is the counterpart of a σ-hole, which is along the extension of a covalent bond to an atom. Both σ-holes and π-holes become more positive (a) in going from the lighter to the heavier atoms in a given Group of...更多

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简介
  • A positive π-hole is a region of positive electrostatic potential that is perpendicular to a portion of a molecular framework.
  • The term “σ-hole” was introduced by Clark et al to describe the regions of positive electrostatic potential that are present on the outer surfaces of many covalentlybonded halogens [1]
  • These positive regions, discovered by Brinck et al in 1992 [2], can interact electrostatically with negative sites on the same or more often other molecules, e.g., lone pairs and π-electrons, giving rise to noncovalent “halogen bonding” [3,4,5].
  • Interactions between these regions of positive electrostatic potential and negative sites on the same or another molecular system are labeled σ-hole bonding;
重点内容
  • A positive π-hole is a region of positive electrostatic potential that is perpendicular to a portion of a molecular framework
  • The term “σ-hole” was introduced by Clark et al to describe the regions of positive electrostatic potential that are present on the outer surfaces of many covalentlybonded halogens [1]
  • For each of the molecules in Table 1 except for H2CO, regions of positive electrostatic potential with VS,max are found above and below the central atom; these are what we label positive π-holes. (In H3CPO2 and H5C6PO2, the phosphorus is considered to be the central atom.) The πholes of SeO2 and H3CPO2 are displayed in Figs. 2 and 3
  • The VS,max associated with the π-holes are given in
  • The geometries and interaction energies ΔE of the complexes formed between the molecules in Table 1 and the Lewis bases HCN and NH3 were determined by three different computational techniques: MP2, M06-2X [31] and B3PW91, in conjunction with the aug-cc-pVDZ basis set
  • The concept of σ-holes has been extended by demonstrating the existence of π-holes, and showing that they have analogous properties
方法
  • The wavefunctions were obtained with Gaussian 09 [29] and the surface potentials, labeled VS(r), with the Wave Function Analysis-Surface Analysis Suite [30].
  • The latter code gives the magnitudes and positions of the locally most positive and most negative values of VS(r), designated VS,max and VS,min; there can be more than one of each on any given molecular surface.
  • The interaction energies were obtained from the molecular energy minima at 0 K with Eq 2: ΔE 1⁄4 EðcomplexÞ À Eðp À hole moleculeÞ
结果
  • Electrostatic potentials

    For each of the molecules in Table 1 except for H2CO, regions of positive electrostatic potential with VS,max are found above and below the central atom; these are what the authors label positive π-holes. (In H3CPO2 and H5C6PO2, the phosphorus is considered to be the central atom.) The πholes of SeO2 and H3CPO2 are displayed in Figs. 2 and 3.
  • For each of the molecules in Table 1 except for H2CO, regions of positive electrostatic potential with VS,max are found above and below the central atom; these are what the authors label positive π-holes.
  • The VS,max associated with the π-holes are given in
结论
  • The concept of σ-holes has been extended by demonstrating the existence of π-holes, and showing that they have analogous properties.
  • A major driving force in both σ-hole and π-hole bonding is the electrostatic interaction between the positive σ- or π-hole and the negative site.
  • Both types of bonds can show a significant gradation, ranging from weak, noncovalent and largely electrostatic to considerably stronger with evidence of some coordinate covalent character
表格
  • Table1: Their magnitudes are comparable to, and in some cases considerably exceed, those of σ-holes [<a class="ref-link" id="c4" href="#r4">4</a>, <a class="ref-link" id="c5" href="#r5">5</a>, <a class="ref-link" id="c13" href="#r13">13</a>,<a class="ref-link" id="c14" href="#r14">14</a>,<a class="ref-link" id="c15" href="#r15">15</a>,<a class="ref-link" id="c16" href="#r16">16</a>, <a class="ref-link" id="c18" href="#r18">18</a>]. As with the latter, π-hole VS,max become more positive in going from the lighter to the heavier atoms in a given column of the periodic table (compare O3, SO2 and SeO2). Note that H2CO does not even have a π-hole, whereas H2SiO has quite a strong one. The VS,max also become more positive as the remainder of the molecule is more electron-withdrawing (compare F2CO and Cl2CO). The sizable difference between the π-hole VS,max of H3CPO2 and H5C6PO2 is probably due to overlapping of the positive π-hole potential and the positive potentials of the nearby methyl hydrogens in H3CPO2. Computed electrostatic potential maxima (VS,max) on 0.001 au molecular surfaces,a above and below indicated atom (π-holes)
  • Table2: Computed properties of π-hole complexes with HCN, using the MP2, M06-2X and B3PW91 methods and the aug-cc-pVDZ basis set
  • Table3: Computed properties of π-hole complexes with NH3, using the MP2, M06-2X and B3PW91 methods and the aug-cc-pVDZ basis set
  • Table4: Computed properties of π-hole complexes of BF3 and BCl3 with HCN and NH3, using the MP2, M06-2X and B3PW91 methods and the aug-cc-pVDZ basis set
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基金
  • TC gratefully acknowledges the generous support of the Deutsche Forschungsgemeinschaft as part of SFB583 (Sonderforschungsbereich 583) “Redox-Active Metal Complexes: Control of Reactivity in Molecular Architecture” and KER the NSF (National Science Foundation) EPSCOR (Experimental Program to Stimulate Competitive Research) Program (Grant number EPS0701525) and the NSF PREM (Partnership for Research & Education in Materials) Program (Grant number DMR-0934115)
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