van der Waals vs. covalent bonding: microwave characterization of a structurally intermediate case

Dvorak, M. A.; Ford, R. S.; Suenram, R. D.; Lovas, Francis J.; Leopold, K. R.

doi:10.1021/ja00027a015

Cited by 101 publications

(114 citation statements)

References 2 publications

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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%

“…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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Section: Resultssupporting

confidence: 74%

Section: Resultsmentioning

confidence: 87%

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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“…Thus, it appears that the intermolecular B-F bond in HF-BF 3 is much like a dative bond in its earliest stages of development. This situation is reminiscent of other systems that we have investigated involving both BF 3 (10,11) and the closely related Lewis acid SO 3 (12,13). For this reason, we have become interested in the hydrogen halide complexes of SO 3 as well and in this paper we report a microwave investigation of HX-SO 3 (X ϭ F, Cl, Br).…”

Section: Introductionmentioning

confidence: 87%

Structures of the van der Waals Isomers of Halosulfuric Acids: Microwave Spectra of HX–SO3(X= F, Cl, Br)

Canagaratna

Phillips

Goodfriend

et al. 1998

Journal of Molecular Spectroscopy

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“…intermediate value of 2.011 for this distance. [43] Perhaps the experimental distance is the vibrationally averaged ground-state distance in a complex with double minima and a small barrier between them. We have pursued this question in complexes of the four BH 3Àn F n boron acids with the Lewis base HCN.…”

Section: Electronic Effects Of Deformationmentioning

confidence: 99%

New Insights into Factors Influencing BN Bonding in X:BH_3−nF_nand X:BH_3−nCl_nfor X=N₂, HCN, LiCN, H₂CNH, NF₃, NH₃andn=0–3: The Importance of Deformation

Alkorta

Elguero

Bene

et al. 2010

Chemistry A European J

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Understanding the bonding in complexes X:BH(3-n)F(n) and X:BH(3-n)Cl(n), for X=N(2), HCN, LiCN, H(2)CNH, NF(3), NH(3) with n=0-3, is a challenging task. The trends in calculated binding energies cannot be explained in terms of any of the usual indexes, including π donation from the halogen lone pairs to the p(π) empty orbital on B, deformation energies, charge capacities, or LUMO energies, which are normally invoked to explain the higher Lewis acidity of BCl(3) relative to BF(3). The results of the high-level G3B3 ab initio calculations reported in this study suggest that the interaction energies of these complexes are determined by a combination of at least three factors. These include the decrease in the electron-accepting ability of B as a result of π donation by the halogen atom, the increase in the electron-acceptor capacity of B due to deformation of the acid, and the large increase in the deformation energy of the acid with increasing halogen substitution. The dominant effects are those derived from the electronic effects of acid deformation. Deformation not only has direct energetic consequences, which are reflected in the large differences between dissociation (D(0)) and interaction (E(int)) energies, but also leads to an enhancement of the intrinsic acidities of BH(3-n)F(n) and BH(3-n)Cl(n) moieties by lowering the LUMO energies to very different extents, consistent with the frontier orbital model of chemical reactivity. Although this lowering depends on both the number and the nature of the halogen substituents, binding energies do not systematically increase or decrease as the number of halogen atoms increases.

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van der Waals vs. covalent bonding: microwave characterization of a structurally intermediate case

Cited by 101 publications

References 2 publications

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

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

Structures of the van der Waals Isomers of Halosulfuric Acids: Microwave Spectra of HX–SO3(X= F, Cl, Br)

New Insights into Factors Influencing BN Bonding in X:BH_3−nF_nand X:BH_3−nCl_nfor X=N₂, HCN, LiCN, H₂CNH, NF₃, NH₃andn=0–3: The Importance of Deformation

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van der Waals vs. covalent bonding: microwave characterization of a structurally intermediate case

Cited by 101 publications

References 2 publications

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

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

Structures of the van der Waals Isomers of Halosulfuric Acids: Microwave Spectra of HX–SO3(X= F, Cl, Br)

New Insights into Factors Influencing BN Bonding in X:BH3−nFnand X:BH3−nClnfor X=N2, HCN, LiCN, H2CNH, NF3, NH3andn=0–3: The Importance of Deformation

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New Insights into Factors Influencing BN Bonding in X:BH_3−nF_nand X:BH_3−nCl_nfor X=N₂, HCN, LiCN, H₂CNH, NF₃, NH₃andn=0–3: The Importance of Deformation