Analysis of electron donor-acceptor complexes: H3N.cntdot.F2, H3N.cntdot.Cl2, and H3N.cntdot.ClF

Røeggen, I.; Dahl, Tor

doi:10.1021/ja00028a017

Cited by 58 publications

(40 citation statements)

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“…[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. In addition to the thousand complexation constants for diiodine, [1] about ...…”

Section: Introductionmentioning

confidence: 99%

“…The concept of a halogen bond [14] has emerged in recent years [15] from the structures of complexes formed between halogen Lewis acids and Lewis bases in the solid state [16][17][18][19][20] and in the gas phase, [21,22] searches in the Cambridge Structural Database of contacts X···E (in which X = halogen and E = atom of groups 15, 16 and 17) [23,24] and theoretical calculations in vacuo. [25][26][27][28][29][30][31] The halogen bond may be defined [32] as the attractive interaction in which halogen atoms function as electropositive sites. In halogen-bonded complexes YÀX···B, Y is preferably an electron-withdrawing group that may be inorganic (e.g., F, Cl, Br, I or N 3 ) or organic (e.g., CF 3 , C N, C 6 F 5 or C CR).…”

Section: Introductionmentioning

confidence: 99%

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

Laurence

Graton

Berthelot

et al. 2011

Chemistry A European J

129

130

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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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Section: Introductionmentioning

confidence: 99%

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

129

130

View full text Add to dashboard Cite

show abstract

“…Recently, several new schemes have been proposed and existing schemes have been modified. [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] For example, Røeggen et al 34,35 developed a novel approach within the framework of an extended geminal model. Glendening and Streitwieser 38 developed natural energy decomposition analysis ͑NEDA͒, a new formalism rooted in the NBO analysis.…”

Section: Introductionmentioning

confidence: 99%

New energy partitioning scheme based on the self-consistent charge and configuration method for subsystems: Application to water dimer system

Korchowiec

Uchimaru²

2000

The Journal of Chemical Physics

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The charge-transfer energy in water dimer is analyzed. The analysis is based on self-consistent charge and configuration method for subsystems (SCCCMS). The SCCCMS, as such, is not restricted to any computational schemes and can be applied at Hartree–Fock (HF), post-HF, and density functional levels of theory. In our approach, the interaction energy is decomposed into deformation (DEF), electrostatic (ES), polarization (P), charge transfer (CT), and exchange (EX) [exchange–correlation (XC)] contributions. The CT energy is derived from the energy surface spanned in the populational space. The intermediate results obtained during construction of this energy surface, such as chemical potentials, hardness and softness parameters, are of particular interest in the theory of chemical reactivity and, thus, these values are discussed as well. The influence of basis set and computational method is analyzed. The numerical values of the energy components obtained at the HF level of theory are compared with those of Kitaura–Morokuma (KM) and reduced variational space (RVS) analyses. It is shown that SCCCMS correctly describes the polarization process. The CT contribution is less dependent on the basis set than KM or RVS scheme and is free from the basis set superposition error (BSSE). It is demonstrated that the CT energy is of little importance for the water dimer. In addition, the amount of CT calculated in our scheme is almost identical to that obtained from the supermolecule calculations.

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“…Extended geminal models have previously been used to study several weakly bonded systems. [8][9][10][11][12][13][14] In particular the van der Waals complex ͑H 2 ͒ 2 has been a serious test of the models. In a recent work by Wind and Ro "eggen, 14 the depth of the isotropic potential was calculated in essentially perfect agreement with experiment.…”

Section: Introductionmentioning

confidence: 99%

An accurate computational model for the study of intermolecular interactions

Røeggen

Almlöf

Ahmadi

et al. 1995

The Journal of Chemical Physics

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Computer simulations of the dielectric properties of water: Studies of the simple point charge and transferrable intermolecular potential models A new computational method within the framework of extended group function models is introduced for describing intermolecular interactions between closed shell systems. The model is size extensive, applicable for any intersystem distance, and has a conceptual structure which facilitates interpretation. The basis set superposition error can be eliminated at the correlation level. Test calculations have been performed on the helium dimer and the helium trimer.

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Analysis of electron donor-acceptor complexes: H3N.cntdot.F2, H3N.cntdot.Cl2, and H3N.cntdot.ClF

Cited by 58 publications

References 0 publications

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

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

New energy partitioning scheme based on the self-consistent charge and configuration method for subsystems: Application to water dimer system

An accurate computational model for the study of intermolecular interactions

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