Ab initio Molecular Orbital Calculations on Group 3 Elements and Their Halides

Amrutha, R.; Sangeetha, L.; Samuel, Deepak; Chandran, P.R. Satheesh

doi:10.1002/chin.200242001

Cited by 2 publications

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“…The calculated BÀXd i s t a n c e s are consistent with covalent bonds between both B atoms and the bridging halogens (see Table 1). The B 2 F 6 ,B 2 Cl 6 ,and B 2 Br 6 -optimized MP2 structures are similar to the previously reported 5,6,15 HartreeÀFock (HF) structures. However, the D 2h MP2 structure of B 2 F 6 is found to be a shallow local minimum rather than a saddle point, as seen for restricted HF.…”

Section: ' Results and Discussionsupporting

confidence: 87%

“…The calculated B–X distances are consistent with covalent bonds between both B atoms and the bridging halogens (see Table ). The B 2 F 6 , B 2 Cl 6 , and B 2 Br 6 -optimized MP2 structures are similar to the previously reported ,, Hartree–Fock (HF) structures. However, the D 2 h MP2 structure of B 2 F 6 is found to be a shallow local minimum rather than a saddle point, as seen for restricted HF. , For the heavier halogens (Cl, Br, I), the van der Waals interaction between terminal halogen atoms becomes increasingly more important, causing the formation of two equivalent C 2 v minima, connected by the D 2 h saddle point.…”

Section: Resultssupporting

confidence: 86%

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Pressure-Induced Formation of Molecular B₂X₄(μ-X)₂ (X = Cl, Br, I) Species

2011

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Boron(III) halides (BX3, where X = F, Cl, Br, I) at ambient pressure conditions exist as strictly monomeric, trigonal-planar molecules. Using correlated ab initio calculations, the three heavier halides (X = Cl, Br, I) are shown to possess B2X4(μ-X)2 local minima, isostructural with the diborane molecule. The calculated dissociation barrier of the B2I4(μ-I)2 species [≈14 kJ/mol with CCSD(T)/cc-pVTZ] may be high enough to allow cryogenic isolation. The remaining dimer structures are more labile, with dissociation barriers of less than 6 kJ/mol. All three dimer species may be stabilized by application of external pressure. Periodic density functional theory calculations predict a new dimer-based P1̅ solid, which becomes more stable than the P63/m monomer-derived solids at 5 (X = I) to 15 (X = Cl) GPa. Metadynamics simulations suggest that B2X4(μ-X)2-based solids are the kinetically preferred product of pressurization of the P63/m solid.

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Section: ' Results and Discussionsupporting

confidence: 87%

Section: Resultssupporting

confidence: 86%

Pressure-Induced Formation of Molecular B₂X₄(μ-X)₂ (X = Cl, Br, I) Species

2011

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“…The neutral dimer di‐μ‐hydroxytetrahydroxy‐diborane B 2 (OH) 4 (μ‐OH) 2 may also present the same structure, this time with the hydroxyl groups acting as bridges . Halogen atoms are similarly able to connect two borane monomers . It is also well‐known that when an additional electron is added to planar BX 3 compounds, which have a formal sp 2 hybridization, this new electron occupies a previously empty p boron orbital, changing the hybridization of the boron atom to nearly sp 3 , with a pyramidal geometry.…”

Section: Introductionmentioning

confidence: 99%

Boron‐Boron One‐Electron Sigma Bonds versus B‐X‐B Bridged Structures

Kusevska

Montero‐Campillo

Mó

et al. 2016

Chemistry A European J

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The existence of one-electron B-B σ bonds, for two different sets of compounds, was investigated by analyzing their electron density with different tools, namely QTAIM, ELF, NCIPLOT, and NBO approaches. Our results indicate that although the generic label "one-electron sigma bond" is often used in the literature, the nature of these bonds varies considerably, or they even do not exist. The [B2 X6 ](-) radical anions give place to true covalent one-electron σ bonds, the stronger the more electronegative is the X substituent. When both boron atoms are substituents in a rigid aromatic moiety, such as naphthalene, to yield 1,8-disubstituted derivatives, two kinds of equilibrium structures are found, those also stabilized through a one-electron σ bond (X=OH, F, Cl, CN) and those stabilized by the formation of B-X-B bridges (X=H, OMe). These 1,8-BX2 naphthalene derivatives can be considered as analogues of 1,8-NX2 naphthalene proton sponges. While the latter are able to stabilize a proton between the two basic sites, the former are able to stabilize an electron between the two electron-deficient B atoms. Interestingly, when all the H atoms attached to B are substituted by phenyl groups no one-electron σ bonds B-B bonds are formed, due to the dispersion of the unpaired electron in the aromatic substituents.

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Ab initio Molecular Orbital Calculations on Group 3 Elements and Their Halides

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 2 publications

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Pressure-Induced Formation of Molecular B₂X₄(μ-X)₂ (X = Cl, Br, I) Species

Pressure-Induced Formation of Molecular B₂X₄(μ-X)₂ (X = Cl, Br, I) Species

Boron‐Boron One‐Electron Sigma Bonds versus B‐X‐B Bridged Structures

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Ab initio Molecular Orbital Calculations on Group 3 Elements and Their Halides

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 2 publications

References 0 publications

Pressure-Induced Formation of Molecular B2X4(μ-X)2 (X = Cl, Br, I) Species

Pressure-Induced Formation of Molecular B2X4(μ-X)2 (X = Cl, Br, I) Species

Boron‐Boron One‐Electron Sigma Bonds versus B‐X‐B Bridged Structures

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Pressure-Induced Formation of Molecular B₂X₄(μ-X)₂ (X = Cl, Br, I) Species

Pressure-Induced Formation of Molecular B₂X₄(μ-X)₂ (X = Cl, Br, I) Species