On the Versatility of BH<sub>2</sub>X (X=F, Cl, Br, and I) Compounds as Halogen‐, Hydrogen‐, and Triel‐Bond Donors: An Ab Initio Study

Bauzá, Antonio

doi:10.1002/cphc.201600683

Cited by 30 publications

(26 citation statements)

References 55 publications

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“…A study into the charge distribution in haloboranes (BH 2 X, X = F, Cl, Br, I) has revealed different types of σ-hole and π-hole non-covalent interactions in the solid-state that exhibit different bonding strengths and geometries. 49 The directional charge distribution on the halogen atoms in [B 12 X 12 ] 2-anions may lead to strong directional bonds to Na + and increase the resistance to reorientational anion disorder in the structure, forcing the polymorphic phase transition to high temperature. In fact, sodium is bound in a deep electrostatic potential well, in-between two halide atoms on the [B 12 2-anion.…”

Section: Discussionmentioning

confidence: 99%

Halogenated Sodium-closo-Dodecaboranes as Solid-State Ion Conductors

et al. 2017

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Sodium compounds containing large weakly coordinating anions are explored as ion conductors. The halogenated sodium-closo-dodecaboranes (Na 2 B 12 Cl 12 , Na 2 B 12 Br 12 , and Na 2 B 12 I 12 ) are all isostructural (Pa-3) at room temperature. These compounds undergo an order-disorder polymorphic transition to Fm-3m where Na + partially occupies two crystallographic sites and [B 12 X 12 ] 2-anions undergo reorientational motion. These dynamic structural properties promote extreme Na + ion conductivity up to 0.162 S/cm at elevated temperature (500 °C). The polymorphic transition temperatures increase down the halogen group (Cl < Br < I). These temperatures are much higher (475, 525 and 570 °C) than for Na 2 B 12 H 12 (266 °C), which could be related to increasing anion size, mass and the anisotropic electron density in the covalently bound halogens (B-X). The halogens may form Na−X interactions with increasing strength and directionality, which restrict dynamic motion until high temperature. The halogenated sodium-closo-dodecaboranes demonstrate excellent thermal stabilities (up to 500 °C) and may facilitate the development of new high temperature ion conductors.

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Section: Discussionmentioning

confidence: 99%

Halogenated Sodium-closo-Dodecaboranes as Solid-State Ion Conductors

et al. 2017

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“…Owing to its important roles in numerous chemical processes, more attention has been paid to triel bonding . Besides the lone‐pair electrons, π‐electrons in aromatic or unsaturated molecules and the single electron in radicals are also taken as Lewis bases in triel bonding.…”

Section: Introductionmentioning

confidence: 99%

“…When BX 3 (X = F, Cl, Br and I) compounds bind with π‐systems including ethene, 1,2‐difluoroethene and perfluoroethene, lone pair–π, halogen and triel bonding interactions are established, but triel bonding is the most favorable among the three types of interactions . Similarly, BH 2 X (X = F, Cl, Br and I) can participate in hydrogen, halogen and triel bonds in its homodimeric systems owing to its dual σ‐ and π‐hole nature . Charge‐assisted triel bonding interactions have also been evidenced in solid‐state chemistry .…”

Section: Introductionmentioning

confidence: 99%

“…[7] Owing to its important roles in numerous chemical processes, [22,23] more attention has been paid to triel bonding. [24][25][26][27][28][29][30][31][32] Besides the lone-pair electrons, π-electrons in aromatic or unsaturated molecules [24][25][26] and the single electron in radicals [27] are also taken as Lewis bases in triel bonding. When BX 3 (X = F, Cl, Br and I) compounds bind with π-systems including ethene, 1,2-difluoroethene and perfluoroethene, lone pair-π, halogen and triel bonding interactions are established, but triel bonding is the most favorable among the three types of interactions.…”

Section: Introductionmentioning

confidence: 99%

“…[26] Similarly, BH 2 X (X = F, Cl, Br and I) can participate in hydrogen, halogen and triel bonds in its homodimeric systems owing to its dual σand π-hole nature. [28] Charge-assisted triel bonding interactions have also been evidenced in solid-state chemistry. [29] Triel bonding exhibits some surprising cooperativity with other types of interactions including hydrogen, [33] halogen, [34] pnicogen [35] and tetrel bonds [36] since the binding distance in the strong triel bond undergoes a prominent contraction.…”

Section: Introductionmentioning

confidence: 99%

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Triel–hydride triel bond between ZX₃ (Z = B and Al; X = H and Me) and THMe₃ (T = Si, Ge and Sn)

Zhang

Wei

et al. 2018

Applied Organom Chemis

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Complexes between THMe3 (T = Si, Ge and Sn) and ZX3 (Z = B and Al; X = H and Me) have been characterized using MP2/aug‐cc‐pVTZ calculations. These complexes are chiefly stabilized by a triel–hydride triel bond with the T–H bond pointing to the π‐hole on the triel atom. The triel–hydride interaction is mainly attributed to the charge transfer from the T–H bond orbital to the empty p orbital of the triel atom. These complexes are very stable with a large interaction energy (>10 kcal mol−1) excluding THMe3···BMe3 (T = Si and Ge), indicating that the sp2‐hydridized triel atom has a strong affinity for the T–H bond. The formation of THMe3···BH3 results in proton transfer, characterized by conversion of orbital interaction and large charge transfer (ca 0.5e). The large deformation is primarily responsible for the abnormally greater interaction energy in THMe3···BH3 (>30 kcal mol−1) than in the AlH3 analogue. Methyl substitution on the triel atom weakens the triel–hydride interaction and causes a larger interaction energy in THMe3···AlMe3 with respect to its BMe3 counterpart. Most of these interactions possess characteristics of covalent bonds. Polarization makes a contribution to the stability of most complexes nearly equivalent to the electrostatic term.

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The Prominence of Facilitator π‐Holes: The Classic N←N Pnictogen Bonding in Nitrobenzene‐Ammonia Dimer with its Structural Elucidation and Experimental Characterization at Low Temperatures

Chandra

Mahapatra

Ramanathan

et al. 2023

Chemistry A European J

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The nitrogen of nitro group is a paradigmatic pnictogen due the presence of a π‐hole and a number of studies have been performed recently on prototypical nitromethane (NM). Homodimers and heterodimers of NM are sustained by π‐hole driven pnictogen bonds hosted by nitrogen. To understand the effect of substitution on this π‐hole and thus the pnictogen bond, heterodimers of nitrobenzene (NB; phenyl substitution in place of methyl) with ammonia (AM) have been probed, as a test case, using matrix isolation infrared spectroscopy and ab initio computations. Of the four structures optimized on the potential energy surface the energetically dominant global minimum, stabilized by π‐hole driven O=N←N pnictogen bonding with co‐operative N−H←O hydrogen bonding, was experimentally identified at low temperatures. A comparison of the pnictogen bonding of NB‐AM dimers with NM counterpart (NM‐AM dimers) divulged the dominance of electrostatic origin of pnictogen bonding in both the class of dimers. The reduced strength of pnictogen bonding in NB‐AM dimers in comparison to NM‐AM dimers was discerned, which has been established to be a consequence of the reduced electrostatic potential at the π‐hole of NB relative to that in NM. The strength of π‐hole driven pnictogen bond was directly correlated with the binding energy and the infrared shifts in the signature vibrational bands of the NB, NM and AM submolecules due to dimerization under matrix isolated conditions at low temperatures.

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On the Versatility of BH₂X (X=F, Cl, Br, and I) Compounds as Halogen‐, Hydrogen‐, and Triel‐Bond Donors: An Ab Initio Study

Cited by 30 publications

References 55 publications

Halogenated Sodium-closo-Dodecaboranes as Solid-State Ion Conductors

Halogenated Sodium-closo-Dodecaboranes as Solid-State Ion Conductors

Triel–hydride triel bond between ZX₃ (Z = B and Al; X = H and Me) and THMe₃ (T = Si, Ge and Sn)

The Prominence of Facilitator π‐Holes: The Classic N←N Pnictogen Bonding in Nitrobenzene‐Ammonia Dimer with its Structural Elucidation and Experimental Characterization at Low Temperatures

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On the Versatility of BH2X (X=F, Cl, Br, and I) Compounds as Halogen‐, Hydrogen‐, and Triel‐Bond Donors: An Ab Initio Study

Cited by 30 publications

References 55 publications

Halogenated Sodium-closo-Dodecaboranes as Solid-State Ion Conductors

Halogenated Sodium-closo-Dodecaboranes as Solid-State Ion Conductors

Triel–hydride triel bond between ZX3 (Z = B and Al; X = H and Me) and THMe3 (T = Si, Ge and Sn)

The Prominence of Facilitator π‐Holes: The Classic N←N Pnictogen Bonding in Nitrobenzene‐Ammonia Dimer with its Structural Elucidation and Experimental Characterization at Low Temperatures

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On the Versatility of BH₂X (X=F, Cl, Br, and I) Compounds as Halogen‐, Hydrogen‐, and Triel‐Bond Donors: An Ab Initio Study

Triel–hydride triel bond between ZX₃ (Z = B and Al; X = H and Me) and THMe₃ (T = Si, Ge and Sn)