Theoretical Study of Complexes and Fluoride Cation Transfer between N<sub>2</sub>F<sup>+</sup>and Electron Donors

Alkorta, Ibón; Solimannejad, Mohammad; Provasi, Patricio F.; Elguero, José

doi:10.1021/jp073112m

Cited by 53 publications

(35 citation statements)

References 62 publications

(82 reference statements)

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“…Since all the adducts and transition structures show a P-C BCP, it is possible to analyze the evolution of the electron density properties between 1.9 and 2.50 Å. Excellent exponential relationships are obtained between the P-C distance with ρ BCP (R 2 = 0.999) and with H BCP (R 2 = 0.998), in agreement with previous reports [56][57][58].…”

Section: Rr'r''p + Co2 (2-5)supporting

confidence: 88%

Solvent and Substituent Effects on the Phosphine + CO2 Reaction

et al. 2018

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A theoretical study of the substituent and solvent effects on the reaction of phosphines with CO2 has been carried out by means of Møller-Plesset (MP2) computational level calculations and continuum polarizable method (PCM) solvent models. Three stationary points along the reaction coordinate have been characterized, a pre-transition state (TS) assembly in which a pnicogen bond or tetrel bond is established between the phosphine and the CO2 molecule, followed by a transition state, and leading finally to the adduct in which the P–C bond has been formed. The solvent effects on the stability and geometry of the stationary points are different. Thus, the pnicogen bonded complexes are destabilized as the dielectric constant of the solvent increases while the opposite happens within the adducts with the P–C bond and the TSs trend. A combination of the substituents and solvents can be used to control the most stable minimum.

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Section: Rr'r''p + Co2 (2-5)supporting

confidence: 88%

Solvent and Substituent Effects on the Phosphine + CO2 Reaction

et al. 2018

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“…Finally, P⋅⋅⋅O interactions in the complexes are found to be very weak, this is revealed by very small ρ BCP values concomitantly with small and positive H BCP values, indicating an absence of any partial covalent character. Exponential relationships between the intermolecular distance and ρ BCP have been found for P⋅⋅⋅P, P⋅⋅⋅N and P⋅⋅⋅C contacts (Figure ) …”

Section: Resultsmentioning

confidence: 99%

“…Exponential relationships between the intermolecular distance and 1 BCP have been found for P···P, P···N and P···C contacts (Figure 1). [39][40][41] Additionally, electron density shift (EDS) maps were calculated and plotted to illustrate and visualise the electron density changes between phosphatranes and CO 2 molecules upon interaction. Two representative systems have been selected, Table 2.…”

Section: Electronic Propertiesmentioning

confidence: 99%

Sequestration of CO₂by Phosphatrane Molecules

et al. 2019

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The stationary points for the reaction between the CO2 and nine different phosphatranes molecules have been characterized by means of MP2 computational methods. Two minima structures have been located: a pnicogen bonded complex where one of the oxygen atoms of CO2 acts as electron donor and an adduct that presents a covalent P−C linkage. The corresponding transition state structure linking the two minima has also been characterized. In gas phase, the pnicogen bonded complex is more stable than the corresponding adduct except in one case. In contrast, the inclusion of the solvent effect (toluene and THF), reverts the stability, being in all cases the different adducts more stable than the pnicogen bonded complexes. The electronic properties of the systems have been analysed with the Quantum Theory of Atoms in Molecules (QTAIM) and Electron Density Shift (EDS) methods.

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“…The obtained interaction energies of the complexes were corrected by the basis set superposition error (BSSE) of full counterpoise (CP) method proposed by the Boys-Bernardi [7], and the zero-point energy (ZPE) evaluation were applied. Natural bond orbital (NBO) analysis [8][9][10][11] was conducted by the NBO program. All calculations were carried out with the Gaussian 03 program [12].…”

Section: Methodsmentioning

confidence: 99%