The Halogen Bond

Cavallo, Gabriella; Metrangolo, Pierangelo; Milani, Roberto; Pilati, Tullio; Priimägi, Arri; Resnati, Giuseppe; Terraneo, Giancarlo

doi:10.1021/acs.chemrev.5b00484

Cited by 3,200 publications

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References 1,127 publications

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“…It is extensively documented that the propensity of a halogen atom to form XBs increases with its molecular weight [10], and that the heavier halogens usually form stronger and shorter XBs than the lighter ones, with both of these behaviors being independent of the XB acceptor. Similar trends are observed when elements of groups 16 and 15 form CBs and PBs, respectively.…”

Section: Oxygen Atoms As Tb Acceptorsmentioning

confidence: 99%

“…σ-Hole interactions [10][11][12] represent a relatively recent entry into the canon of weak bonds [13][14][15], but following the seminal papers of P. Politzer et al [16,17], these interactions rapidly became popular targets for studies in this field [15,[18][19][20]. A covalently bonded atom characteristically has a region of low electron density, known as the Bσ-hole,ŵ hich is usually located along the extension of the covalent bond but on the opposite side of the atom to the bond.…”

Section: Introductionmentioning

confidence: 99%

“…A growing consensus is emerging among chemists that these interactions should be named according to the group of the periodic table that the electrophilic atom belongs to [22,23]. Halogen bonds (XBs) [10,24], namely interactions where an atom of a group 17 element is the electrophilic site, represent the best known subset of σ-hole interactions. Chalcogen bonds (CBs) have been studied in silico [25,26] and in the solid [27], liquid [28], and gas [29] phases.…”

Section: Introductionmentioning

confidence: 99%

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Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

et al. 2018

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Modeling indicates the presence of a region of low electronic density (a Bσ-hole^) on group 14 elements, and this offers an explanation for the ability of these elements to act as electrophilic sites and to form attractive interactions with nucleophiles. While many papers have described theoretical investigations of interactions involving carbon and silicon, such investigations of the heavier group 14 elements are relatively scarce. The purpose of this review is to rectify, to some extent, the current lack of experimental data on interactions formed by germanium and tin with nucleophiles. A survey of crystal structures in the Cambridge Structural Database is reported. This survey reveals that close contacts between Ge or Sn and lone-pair-possessing atoms are quite common, they can be either intra-or intermolecular contacts, and they are usually oriented along the extension of the covalent bond formed by the tetrel with the most electron-withdrawing substituent. Several examples are discussed in which germanium and tin atoms bear four carbon residues or in which halogen, oxygen, sulfur, or nitrogen substituents replace one, two, or three of those carbon residues. These close contacts are assumed to be the result of attractive interactions between the involved atoms and afford experimental evidence of the ability of germanium and tin to act as electrophilic sites, namely tetrel bond (TB) donors. This ability can govern the conformations and the packing of organic derivatives in the solid state. TBs can therefore be considered a promising and robust tool for crystal engineering.

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Section: Oxygen Atoms As Tb Acceptorsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

et al. 2018

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“…Arguably the best studied σ‐hole interaction is the halogen bond,9 which has found elegant applications in organocatalysis (Figure 2 a, green) 2. Possibly owing to higher steric demands, non‐covalent chalcogen bonding in solution has only recently received increased attention,10 and was applied to non‐covalent catalysis only last year (Figure 2 a, red) 11, 12.…”

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Catalysis with Pnictogen, Chalcogen, and Halogen Bonds

et al. 2018

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Halogen‐ and chalcogen‐based σ‐hole interactions have recently received increased interest in non‐covalent organocatalysis. However, the closely related pnictogen bonds have been neglected. In this study, we introduce conceptually simple, neutral, and monodentate pnictogen‐bonding catalysts. Solution and in silico binding studies, together with high catalytic activity in chloride abstraction reactions, yield compelling evidence for operational pnictogen bonds. The depth of the σ holes is easily varied with different substituents. Comparison with homologous halogen‐ and chalcogen‐bonding catalysts shows an increase in activity from main group VII to V and from row 3 to 5 in the periodic table. Pnictogen bonds from antimony thus emerged as by far the best among the elements covered, a finding that provides most intriguing perspectives for future applications in catalysis and beyond.

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“…While during the past two decades HB has been widely exploited in anion receptor design, halogen bonding (XB),24, 25, 26, 27 the attractive highly directional interaction between an electron‐deficient halogen atom and a Lewis base, has only recently begun to be utilised for anion recognition. Of the relatively few examples of XB anion receptors reported to date, it is noteworthy that all display promising, and significantly contrasting, anion recognition behaviour when compared to HB analogues, by virtue of their comparable bond strengths and more strict linear geometry preference 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42.…”

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Selective Nitrate Recognition by a Halogen‐Bonding Four‐Station [3]Rotaxane Molecular Shuttle

et al. 2016

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The synthesis of the first halogen bonding [3]rotaxane host system containing a bis‐iodo triazolium‐bis‐naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo‐triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion–rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the 1H NMR anion binding results.

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The Halogen Bond

Cited by 3,200 publications

References 1,127 publications

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

Catalysis with Pnictogen, Chalcogen, and Halogen Bonds

Selective Nitrate Recognition by a Halogen‐Bonding Four‐Station [3]Rotaxane Molecular Shuttle

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