The identification of the classical donor–acceptor complex H<sub>3</sub>N–BF<sub>3</sub>in the gas phase

Legon, A. C.; Warner, H. E.

doi:10.1039/c39910001397

Cited by 45 publications

(37 citation statements)

References 16 publications

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“…Similar to NH 3 BH 3 , the BN bond length in NH 3 BF 3 is likely 0.06-0.10 Å larger than the hitherto assumed value of r(BN) = 1.59 Å [12,78] in agreement with calculated values.…”

Section: Structures Of Polyatomic Gas-phase Moleculessupporting

confidence: 76%

Quantum chemical B3LYP/cc-pvqz computation of ground-state structures and properties of small molecules with atoms of Z ≤ 18 (hydrogen to argon)(IUPAC Technical Report)

Janoschek

2001

Pure and Applied Chemistry

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Republication or reproduction of this report or its storage and/or dissemination by electronic means is permitted without the need for formal IUPAC permission on condition that an acknowledgmentAbstract: Since density functional theory (DFT) achieved a remarkable breakthrough in computational chemistry, the important general question "How reliable are quantum chemical calculations for spectroscopic properties?" should be answered anew. In this project, the most successful density functionals, namely the Becke B3LYP functionals, and the correlation-consistent polarized valence quadruple zeta basis sets (cc-pvqz) are applied to small molecules. In particular, the complete set of experimentally known diatomic molecules formed by the atoms H to Ar (these are 214 species) is uniformly calculated, and calculated spectroscopic properties are compared with experimental ones. Computationally demanding molecules, such as open-shell systems, anions, or noble gas compounds, are included in this study. Investigated spectroscopic properties are spectroscopic ground state, equilibrium internuclear distance, harmonic vibrational wavenumber, anharmonicity, vibrational absolute absorption intensity, electric dipole moment, ionization potential, and dissociation energy. The same computational method has also been applied to the ground-state geometries of 56 polyatomic molecules up to the size of benzene. Special sections are dedicated to nuclear magnetic resonance (NMR) chemical shifts and isotropic hyperfine coupling constants. Each set of systems for a chosen property is statistically analyzed, and the above important question "How reliable...?" is mathematically answered by the mean absolute deviation between calculated and experimental data, as well as by the worst agreement. In addition to presentation of numerous quantum chemically calculated spectroscopic properties, a corresponding updated list of references for experimentally determined properties is presented.

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“…Similar to NH 3 BH 3 , the BN bond length in NH 3 BF 3 is likely 0.06-0.10 Å larger than the hitherto assumed value of r(BN) = 1.59 Å [12,78] in agreement with calculated values.…”

Section: Structures Of Polyatomic Gas-phase Moleculessupporting

confidence: 76%

Quantum chemical B3LYP/cc-pvqz computation of ground-state structures and properties of small molecules with atoms of Z ≤ 18 (hydrogen to argon)(IUPAC Technical Report)

Janoschek

2001

Pure and Applied Chemistry

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“…Other parameters are presented in Table 1. The calculated geometric parameters are quite comparable with experimental values [32][33][34][35]. Results demonstrate that the 'B-F' bond stretches on formation of the supermolecule.…”

Section: Resultssupporting

confidence: 74%

“…Such stretching of the B-F bond of BF 3 upon planar (D 3h ) to pyramidal (C 3v ) reorganization of its structure is quite expected due to the resulting elimination of B-F double bond character already observed by Ghosh et al [6] and others [32][33][34][35]44]. From Table 2 it is clear that the energy of D 3h to C 3v reorganization of BF 3 is quite high, consistent with the suggestion that the planar to pyramidal evolution of the molecular shape is associated with the elimination of the π bond between B and F and stretching of B-F bond [6,[32][33][34][35]45]. The reorganization in the NH 3 moiety before the adduct formation is insignificantly small.…”

Section: Resultsmentioning

confidence: 87%

“…Atomic charge on N Atomic charge on H That the height of the barrier to the internal rotation in the donor-acceptor complex formed between NH 3 and BF 3 would be very small was predicted by Legon and Warner [33], in the course of their study of the microwave spectrum of rotational transition in the molecule. Now let us consider the pattern of organization and reorganization of charge density within the molecule under the dynamics of internal rotation of the molecule because, the pattern of charge density reorganization with the evolution of molecular conformation has a significant role on the origin and the development of the height of the barrier to internal rotation.…”

Section: Conformational Analysis Of F 3 B-nhmentioning

confidence: 99%

“…A number of reports of study of the electronic structure, binding and formation of F 3 B-NH 3 have appeared [32][33][34][35], but it seems that the study of mechanism of charge transfer interaction has not been taken up by any group. There is no report of any attempt of a density function rationale of charge transfer interaction between BF 3 and NH 3 during the formation of the supermolecule.…”

Section: Introductionmentioning

confidence: 99%

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Molecular Orbital and Density Functional Study of the Formation, Charge Transfer, Bonding and the Conformational Isomerism of the Boron Trifluoride (BF3) and Ammonia (NH3) Donor-Acceptor Complex

Ghosh

Bhattacharyya

2004

IJMS

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:The formation of the F 3 B-NH 3 supermolecule by chemical interaction of its fragment parts, BF 3 and NH 3 , and the dynamics of internal rotation about the 'B-N' bond have been studied in terms of parameters provided by the molecular orbital and density functional theories. It is found that the pairs of frontier orbitals of the interacting fragments have matching symmetry and are involved in the charge transfer interaction. The donation process stems from the HOMO of the donor into the LUMO of the acceptor and simultaneously, back donation stems from the HOMO of acceptor into the LUMO of the donor. The density functional computation of chemical activation in the donor and acceptor fragments, associated with the physical process of structural reorganization just prior to the event of chemical reaction, indicates that BF 3 becomes more acidic and NH 3 becomes more basic, compared to their separate equilibrium states. Theoretically it is observed that the chemical reaction event of the formation of the supermolecule from its fragment parts is in accordance with the chemical potential equalization principle of the density functional theory and the electronegativity equalization principle of Sanderson. The energetics of the chemical reaction, the magnitude of the net charge transfer and the energy of the newly formed bond are quite consistent, both internally and with the principle of maximum hardness, PMH. The Int. J. Mol. Sci. 2004, 2 240 dynamics of the internal rotation of one part with respect to the other part of the supermolecule about the 'B-N' bond mimics the pattern of the conformational isomerism of the isostructural ethane molecule. It is also observed that the dynamics and evolution of molecular conformations as a function of dihedral angles is also in accordance with the principle of maximum hardness, PMH. Quite consistent with spectroscopic predictions, the height of the molecule's barrier to internal rotation is very small. A rationale for the low height of the barrier has been put forward in terms of the energy partitioning analysis. On the question of origin of the barrier to internal rotation, we conclude that the conformational barrier to internal rotation does not originate from a particular region of the molecule, but rather it is a result of the subtle conjoint interplay of a number of opposing effects of one-and two-center bonded and nonbonded energy terms involving the entire skeleton of the molecule.

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Use of 5,10‐Disubstituted Dibenzoazaborines and Dibenzophosphaborines as Cyclic Supports of Frustrated Lewis Pairs for the Capture of CO₂

et al. 2022

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The reactivity of 5,10-disubstituted dibenzoazaborines and dibenzophosphaborines towards carbon dioxide was studied at the DFT, M06-2X/def2-TZVP, computational level. The profile of this reaction comprises of three stationary points: the prereactive complex and adduct minima and the transition state(TS) linking both minima. Initial results show that dibenzoazaborines derivatives are less suitable to form adducts with CO 2 than dibenzophosphaborine systems. The influence of the basicity on the P atom and the acidity on the B center of the dibenzophosphaborine in the reaction with CO 2 was also explored. Thus, an equation was developed relating the properties (acidity, basicity and boron hybridization) of the isolated dibenzophosphaborine derivatives with the adduct energy. We found that modulation of the boron acidity allows to obtain more stable adducts than the pre-reactive complexes and isolated monomers.[a] M.

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The identification of the classical donor–acceptor complex H₃N–BF₃in the gas phase

Cited by 45 publications

References 16 publications

Quantum chemical B3LYP/cc-pvqz computation of ground-state structures and properties of small molecules with atoms of Z ≤ 18 (hydrogen to argon)(IUPAC Technical Report)

Quantum chemical B3LYP/cc-pvqz computation of ground-state structures and properties of small molecules with atoms of Z ≤ 18 (hydrogen to argon)(IUPAC Technical Report)

Molecular Orbital and Density Functional Study of the Formation, Charge Transfer, Bonding and the Conformational Isomerism of the Boron Trifluoride (BF3) and Ammonia (NH3) Donor-Acceptor Complex

Use of 5,10‐Disubstituted Dibenzoazaborines and Dibenzophosphaborines as Cyclic Supports of Frustrated Lewis Pairs for the Capture of CO₂

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The identification of the classical donor–acceptor complex H3N–BF3in the gas phase

Cited by 45 publications

References 16 publications

Quantum chemical B3LYP/cc-pvqz computation of ground-state structures and properties of small molecules with atoms of Z ≤ 18 (hydrogen to argon)(IUPAC Technical Report)

Quantum chemical B3LYP/cc-pvqz computation of ground-state structures and properties of small molecules with atoms of Z ≤ 18 (hydrogen to argon)(IUPAC Technical Report)

Molecular Orbital and Density Functional Study of the Formation, Charge Transfer, Bonding and the Conformational Isomerism of the Boron Trifluoride (BF3) and Ammonia (NH3) Donor-Acceptor Complex

Use of 5,10‐Disubstituted Dibenzoazaborines and Dibenzophosphaborines as Cyclic Supports of Frustrated Lewis Pairs for the Capture of CO2

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Product

Resources

About

The identification of the classical donor–acceptor complex H₃N–BF₃in the gas phase

Use of 5,10‐Disubstituted Dibenzoazaborines and Dibenzophosphaborines as Cyclic Supports of Frustrated Lewis Pairs for the Capture of CO₂