On the nature of halogen bond – The Kohn–Sham molecular orbital approach

Palusiak, Marcin

doi:10.1016/j.theochem.2010.01.022

Cited by 123 publications

(111 citation statements)

References 37 publications

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“…Note, however, that we consider the MP2-SCF densities as an approximation of the lowest reliability of those taken into account since these densities in fact are not consistent with equilibrium geometries estimated at the MP2 post-SCF level of calculations. Therefore, the significantly stronger X-bonds formed by F 3 C-Cl as compared with H 3 C-Cl [28], cannot be explained merely on the basis of larger anisotropy of Cl atom in the former. In this case, another mechanism must be responsible for the additional strengthening of the X-bond, which may be connected with the charge transfer from Lewis base center into the inner region of Lewis acid center and not directly on the halogen atom (Cl in that case).…”

Section: Resultsmentioning

confidence: 97%

“…As a result, the electrostatic nature of X-bonding was proposed [17]. However, in the literature, there are several reports based on the different interaction energy decompositions, in which it was shown that not necessarily electrostatic interaction, but HOMO-LUMO charge transfer and polarization [28], induction, and/or dispersion [27,29,30] are responsible for X-bonding. Unfortunately, each type of the interaction energy decomposition is always connected with an arbitrary procedure, and the components of interaction energy obtained within the framework of different schemes are often incomparable.…”

Section: Introductionmentioning

confidence: 99%

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The shape of the halogen atom—anisotropy of electron distribution and its dependence on basis set and method used

Bankiewicz

Palusiak

2012

Struct Chem

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A search through Crystal Structure Database was performed and the distances in contacts of XÁÁÁN,O, XÁÁÁH(N,O), and XÁÁÁC type were collected together with the information on spatial arrangement of the interacting fragments. A detailed statistical analysis showed that the shape of the halogen atom cannot be simply concluded on the basis of interatomic distances in crystal state although originally the concept of anisotropic charge distribution around halogen nuclei was postulated on the basis of such an analysis. It was proven that the conclusions in that case strongly depend on the type of center interacting with the halogen atom. Therefore, it was postulated that the shape of the halogen atom can be estimated for the unperturbed (due to intermolecular interactions) halogen atom. For this purpose, a method was provided to make possible a numerical quantification of the anisotropy of the halogen atom on the basis of electron density measurements performed within the framework of Atoms in Molecules Quantum Theory. The anisotropy of Cl and Br atoms in H 3 C-X and F 3 C-X (X=Cl, Br) was estimated for MP2 and DFT-B3LYP methods and several different basis sets. The influence of the method and the basis set on the degree of anisotropic distribution of electron density around halogen nuclei was discussed.Keywords Halogen bond Á The shape of the atom Á QTAIM Á DFT Á MP2 Á Basis set

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Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

The shape of the halogen atom—anisotropy of electron distribution and its dependence on basis set and method used

Bankiewicz

Palusiak

2012

Struct Chem

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“…By one procedure, the primary stabilizing components were found to be electrostatics and dispersion [67]. The other energy dissection scheme concluded, for the same complexes, that charge transfer and polarization are dominant and that electrostatics contributes only "slightly" [68]. (So what causes the polarization?…”

Section: The Nature Of σ-Hole Interactionsmentioning

confidence: 99%

σ-Hole Bonding: A Physical Interpretation

Politzer

Murray

Clark

2014

Topics in Current Chemistry

148

116

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The anisotropic electronic densities of covalently-bonded Group IV-VII atoms frequently give rise to regions of positive electrostatic potential on the extensions of covalent bonds to these atoms. Through such positive "σ-holes," the atoms can interact attractively and highly directionally with negative sites such as the lone pairs of Lewis bases, anions, π electrons, etc. In the case of Group VII this is called "halogen bonding." Hydrogen bonding can be viewed as a less directional subset of σ-hole interactions. Since positive σ-holes often exist in conjunction with regions of negative potential, the atoms can also interact favorably with positive sites. In accordance with the Hellmann-Feynman theorem, all of these interactions are purely Coulombic in nature (which encompasses polarization and dispersion). The strength of σ-hole bonding increases with the magnitudes of the potentials of the positive σ-hole and the negative site; their polarizabilities must sometimes also be taken explicitly into account.

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“…The respective contributions of these interactions are still a matter of debate. [23,25,27,29,[33][34][35][36][37][38][39] Halogen bonding has recently been recognised as a significant interaction in molecular recognition and self-assembly processes, [40,41] and is therefore employed for a wide range of applications in materials, [42][43][44][45] synthetic [46][47][48] and medicinal chemistry. [49][50][51][52] Concerning the fundamentals of halogen bonding, recent studies have focused mainly on structural determinations [18][19][20][21][22] and on quantum mechanical calculations of the bond energy in vacuo at 0 K. [25][26][27][28][29][30][31][53][54][55][56][57][58][59][60] The experimental knowledge of the thermodynamics of the halogen bond at room temperature in solution shows a marked contrast between inorganic and organic halogen-bond donors.…”

Section: Introductionmentioning

confidence: 99%

The Diiodine Basicity Scale: Toward a General Halogen‐Bond Basicity Scale

Laurence

Graton

Berthelot

et al. 2011

Chemistry A European J

124

129

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The new diiodine basicity scale pK(BI2) is quasi-orthogonal to most known Lewis basicity scales (hydrogen-bond, dative-bond and cation basicity scales). The diiodine basicity falls in the sequence N>P≈Se>S>I≈O>Br>Cl>F for the iodine-bond acceptor atomic site and SbO≈NO≈AsO>SeO>PO>SO>C=O>-O->SO(2) or PS≫-S->C=S≫N=C=S for the functionality of oxygen or sulfur bases. Substituent effects are quantified through linear free energy relationships, which allow the calculation of individual complexation constants for each site of polybases and thus the classification of aromatic ethers as carbon π bases and of aromatic amines, thioethers and selenoethers as N, S and Se bases, respectively. The pK(BI2) values of nBu(3)N(+)-N(-)C≡N, 2-aminopyridine and 1,10-phenanthroline reveal a superbasic nitrile, a hydrogen-bond-assisted iodine bond and a two-centre iodine bond, respectively. The diiodine basicity scale is a general inorganic but family-dependent organic halogen-bond basicity scale because organic halogen-bond donors such as IC≡N and ICF(3) have a stronger electrostatic character than I(2). The family independence can be restored by the addition of an electrostatic parameter, either the experimental pK(BHX) hydrogen-bond basicity scale or the computed minimum electrostatic potential.

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On the nature of halogen bond – The Kohn–Sham molecular orbital approach

Cited by 123 publications

References 37 publications

The shape of the halogen atom—anisotropy of electron distribution and its dependence on basis set and method used

The shape of the halogen atom—anisotropy of electron distribution and its dependence on basis set and method used

σ-Hole Bonding: A Physical Interpretation

The Diiodine Basicity Scale: Toward a General Halogen‐Bond Basicity Scale

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