Halogen Bonding with Dihalogens and Interhalogens

Pennington, William T.; Hanks, Timothy W.; Arman, Hadi D.

doi:10.1007/430_2007_067

Cited by 70 publications

(77 citation statements)

References 180 publications

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“…In the B···IÀI complex, the three dots denote a halogen bond. 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.…”

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

126

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%

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

Laurence

Graton

Berthelot

et al. 2011

Chemistry A European J

126

130

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“…For example, in the review paper "Halogen Bonding with Dihalogens and Interhalogens", 4 Pennington pointed out that sulfur-based XB acceptors are the most commonly encountered. It combines indeed the characteristic anisotropic charge distribution on the halogen atoms, the so-called σ-hole concept introduced by P. Politzer and J. S. Murray, 3 and the directionality of the amine lone pair.…”

Section: Introductionmentioning

confidence: 99%

CS⋯I halogen bonding interactions in crystalline iodinated dithiole-2-thiones and thiazole-2-thiones

et al. 2016

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The propensity of the sp 2 sulfur atom in thiones to act as a halogen bond (XB) acceptor is well established with dihalides (I 2 , IBr or ICl) as XB donors, but has been more rarely explored with organic XB donors. The crystal structures of four iodinated heterocycles, namely, the mono-and diiodo derivatives of 1,3-dithiole-2-thione and N-ethylthiazole-2-thione, offer an opportunity to evaluate the strength and directionality of such C-I⋯S interactions. We describe here the original synthesis of 3-ethyl-5-iodothiazole-2Ĳ3H)-thione and 3-ethyl-4,5-diiodothiazole-2Ĳ3H)-thione and the solid state structures of the four compounds, with specific attention to the halogen bonds (C-I⋯SC) and hydrogen bonds (C-H⋯I,S) taking place in the crystals, in connection with the peculiarities of the calculated electrostatic surface potential (ESP) of the four molecules. The thione sulfur atoms in thiazole-2-thiones appear as better XB acceptors than in dithiole-2-thiones, with a notable deformation of the charge concentration area. The mono-iodinated derivatives, 4-iodo-1,3-dithiole-2-thione and 3-ethyl-5-iodothiazole-2-thione, are characterized by hydrogen atoms with positive extremum of the electrostatic surface potential comparable to those of the neighboring iodine atoms, illustrating the parallelism between C-I⋯S halogen bonds and the so-called weak C-H⋯I,S hydrogen bonds. CrystEngCommThis journal is

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“…[13] Reactions between dihalogen molecules XY and simple Lewis bases B are of fundamental interest in organic and inorganic chemistry and, consequently, have featured prominently in the history of these subjects. When XY is F 2 or ClF, such reactions can be especially violent. Accordingly, it is a challenge for the chemist to isolate and characterize in detail the species produced in the initial, prereactive encounter of B/XY pairs in a potentially reactive mixture.…”

Section: Introductionmentioning

confidence: 97%

“…[1][2][3][4][5] Metrangolo, Resnati, and co-workers have demonstrated convincingly that halogen bonding is a general strategy for crystal engineering and for the noncovalent assembly of new materials; this has sparked new levels of interest in this interaction. [1,2,5] It is now well established and widely recognized that halogen bonding involves a region of positive electrostatic potential on the tip of a halogen atom interacting with the negative potential of a Lewis base. The region of positive potential on the surface of a halogen is often described as a positive s hole [6] and has also been termed the electropositive crown.…”

Section: Introductionmentioning

confidence: 99%

The Role of Molecular Electrostatic Potentials in the Formation of a Halogen Bond in Furan⋅⋅⋅XY and Thiophene⋅⋅⋅XY Complexes

Zeng¹,

Zhang²,

Li³

et al. 2011

ChemPhysChem

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The halogen bonding of furan⋅⋅⋅XY and thiophene⋅⋅⋅XY (X=Cl, Br; Y=F, Cl, Br), involving σ- and π-type interactions, was studied by using MP2 calculations and quantum theory of "atoms in molecules" (QTAIM) studies. The negative electrostatic potentials of furan and thiophene, as well as the most positive electrostatic potential (V(S,max) ) on the surface of the interacting X atom determined the geometries of the complexes. Linear relationships were found between interaction energy and V(S,max) of the X atom, indicating that electrostatic interactions play an important role in these halogen-bonding interactions. The halogen-bonding interactions in furan⋅⋅⋅XY and thiophene⋅⋅⋅XY are weak, "closed-shell" noncovalent interactions. The linear relationship of topological properties, energy properties, and the integration of interatomic surfaces versus V(S,max) of atom X demonstrate the importance of the positive σ hole, as reflected by the computed V(S,max) of atom X, in determining the topological properties of the halogen bonds.

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Halogen Bonding with Dihalogens and Interhalogens

Cited by 70 publications

References 180 publications

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

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

CS⋯I halogen bonding interactions in crystalline iodinated dithiole-2-thiones and thiazole-2-thiones

The Role of Molecular Electrostatic Potentials in the Formation of a Halogen Bond in Furan⋅⋅⋅XY and Thiophene⋅⋅⋅XY Complexes

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