Synthesis, microwave spectrum, and structure of ArBF3, BF3CO, and N2BF3

Janda, Kenneth C.; Bernstein, L. S.; Steed, J. M.; Novick, Stewart E.; Klemperèr, William

doi:10.1021/ja00494a008

Cited by 140 publications

(82 citation statements)

References 6 publications

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“…However, as the amount of surrounding molecules increases, and hence more hydrogen bonds are formed between the dimer unit and surrounding H-atoms, the remaining two angles also display differences. Defining the NBF angle containing the F-atom hydrogen bonded to the opposite molecule in the dimer as the inward pointing angle, and the two remaining angles as the outward pointing angles, a clear illustration of the surrounding molecule effect is the difference between the outward pointed NBF angles in the (HCN-BF 3 ) 6 and (HCN-BF 3 ) 8 systems. As seen in Figure 1, the latter system differs from the former system by the two molecules labeled 8.…”

Section: Resultsmentioning

confidence: 99%

Crystalline Effects on the Properties of the Dative Bond: A Computational Study of HCN−BF₃

Venter

Dillen

2004

J. Phys. Chem. A

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The changes in molecular structure associated with the crystallization of the donor-acceptor complex HCN-BF 3 are studied using density functional theory. Short-range dipole-dipole interactions have been attributed to be one of the main causes of the 0.84 Å shortening of the B-N bond in the crystal phase compared to the gas phase. Natural bond orbital analysis is used to obtain information regarding the electron distribution and possible delocalization effects. The lone pair on the fluorine atoms shows significant delocalization toward the boron-nitrogen antibonding orbital, leading to substantial structural changes occurring that can be manipulated by increasing or decreasing the degree of overlap. Because the overlap is dependent on the position of the fluorine atom, the steric and electronic influences created by the surroundings of a molecular unit in the crystal are of considerable importance when the experimentally observed changes are explained.

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Section: Resultsmentioning

confidence: 99%

Crystalline Effects on the Properties of the Dative Bond: A Computational Study of HCN−BF₃

Venter

Dillen

2004

J. Phys. Chem. A

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“…Results demonstrate that the 'B-F' bond stretches on formation of the supermolecule. 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].…”

Section: Resultsmentioning

confidence: 68%

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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“…F 3 BCO À200 [23] 7.6 [64] 2.89 [67] 2151 [68] (C 6 F 5 ) 3 BCO À100 [22] (38) [65] (1.61) [65] 2230 [22] (CF 3 ) 3 BCO 0 [22] 112 [22] 1.62 [22] 2269 [22] H 3 BCO 10 [22] 90…”

Section: Reaktionen Von Trifluormethylsubstituenten Anmentioning

confidence: 99%

Trifluormethylborane und ‐borate – neue Synthesestrategien und Anwendungen

2007

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Mit der Synthese des [B(CF3)4]−‐Anions setzte eine neue Entwicklung im Bereich der Trifluormethylborchemie ein. Während die bisher beschriebenen (CF3)nB‐Derivate (n=1–3) ausschließlich durch die Übertragung von CF3‐Gruppen hergestellt wurden, gelang die Synthese des [B(CF3)4]−‐Anions durch die Fluorierung des [B(CN)4]−‐Anions mit ClF oder ClF3 in wasserfreier HF. Aufgrund seiner thermischen und chemischen Stabilität ist das [B(CF3)4]−‐Anion ein attraktives schwach koordinierendes Anion. In konzentrierter Schwefelsäure wird jedoch eine der vier CF3‐Gruppen zu einem CO‐Liganden solvolysiert und das neutrale Carbonylboran (CF3)3BCO erhalten. Es zeigte sich, dass diese Verbindung ein vielseitiger Synthesebaustein ist, und zahlreiche Reaktionen wurden inzwischen untersucht. Nucleophile addieren bevorzugt an das C‐Atom des CO‐Liganden. Beispiele neuer Derivate sind die Anionen [(CF3)3BCPnic]− (Pnic=N, P, As). Es ist aber auch ein Ligandenaustausch unter Abgabe von CO beispielsweise zu (CF3)3BNCH möglich. Schließlich ist (CF3)3BCO eine Komponente der konjugierten Brønsted‐Lewis‐Supersäure HF/(CF3)3BCO.

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Synthesis, microwave spectrum, and structure of ArBF3, BF3CO, and N2BF3

Cited by 140 publications

References 6 publications

Crystalline Effects on the Properties of the Dative Bond: A Computational Study of HCN−BF₃

Crystalline Effects on the Properties of the Dative Bond: A Computational Study of HCN−BF₃

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

Trifluormethylborane und ‐borate – neue Synthesestrategien und Anwendungen

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Synthesis, microwave spectrum, and structure of ArBF3, BF3CO, and N2BF3

Cited by 140 publications

References 6 publications

Crystalline Effects on the Properties of the Dative Bond: A Computational Study of HCN−BF3

Crystalline Effects on the Properties of the Dative Bond: A Computational Study of HCN−BF3

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

Trifluormethylborane und ‐borate – neue Synthesestrategien und Anwendungen

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Crystalline Effects on the Properties of the Dative Bond: A Computational Study of HCN−BF₃

Crystalline Effects on the Properties of the Dative Bond: A Computational Study of HCN−BF₃