Reactivity and Thermal Stability of Hexafluorides

Galkin, N.P.; Tumanov, Yu. N.

doi:10.1070/rc1971v040n02abeh001902

Cited by 23 publications

(11 citation statements)

References 2 publications

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“…where E s ' is a steric constant of substituents X. [35,36] The foregoing provides the basis for the elucidation of substituent effects, which define the BDEs. In connection with this, it is appropriate to dwell briefly on the excess charge q on the reaction (indicator) center R C of the charged non-classic narrow series XBR C q and XR C q .…”

Section: Calculation Procudurementioning

confidence: 99%

Bond dissociation energies in organometallic systems: substituent effects

Кузнецова

Egorochkin

Хамалетдинова

et al. 2014

J. Phys. Org. Chem.

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A knowledge of the factors determining the magnitude of the bond dissociation enthalpy (BDE) is of importance to the advancement of theoretical organometallic chemistry and from the practical standpoint. The central atom and the substituents bound to it influence the BDE values; however, the interplay between the BDE and the substituent effects remains unknown. In this work, the literature data on substituent influence on the BDE of lithium, sodium, copper, silver, mercury, aluminium, gallium, silicon, germanium, tin, lead, phosphorus, antimonium, chromium, iron, cobalt, nickel, rhodium, and iridium compounds (37 series) have been analyzed, using the correlation analysis. Generally, the BDE values were first established to depend on the joint influence of the inductive, resonance, polarizability, and steric effects of substituents. The contribution of the polarizability effect ranges up to about 40%. Copyright © 2014 John Wiley & Sons, Ltd.

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Section: Calculation Procudurementioning

confidence: 99%

Bond dissociation energies in organometallic systems: substituent effects

Кузнецова

Egorochkin

Хамалетдинова

et al. 2014

J. Phys. Org. Chem.

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“…(In the following this reaction will be referred as the key reaction.) For this reason, UF 6 has become a prototype molecule for a considerable amount of experimental − and theoretical − work.…”

Section: Introductionmentioning

confidence: 99%

A Relativistic Density Functional Study on the Uranium Hexafluoride and Plutonium Hexafluoride Monomer and Dimer Species

et al. 1998

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A study on the UF 6 monomer and dimer was carried out within the density functional method. The U-F distance in the UF 6 monomer was optimized at different levels of theory, pointwise, assuming octahedral geometry, (1) by using an all-electron basis for both U and F in a nonrelativistic calculation; (2) by using a relativistic effective core potential (RECP) on U and nonrelativistic effective core potential (ECP) on the fluorines; and (3) by using RECP on the U atom and an all-electron basis on the F atoms. Atomization energies of 23.11, 33.92, and 35.66 eV were obtained at the three levels, respectively. Relativistic effects lead to about a 50% increase in the atomization energy. For the UF 6 dimer, the potential energy curve, as a function of the intermolecular U-U distance, was computed at level 2, and the rotational barrier between the two monomers was determined. Similar calculations were performed on the corresponding PuF 6 species. Comparisons are made with experiment and other theoretical studies, where available.

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“…where E S ′ is a steric constant of substituents X. [63,64] For each individual narrow reaction (indicator) series, there is one, and only one, so-called best fitting correlation equation (BFCE). BFCE differs from any other equations for a given series.…”

Section: Calculation Proceduresmentioning

confidence: 99%

Noncovalent interactions involving aromatic rings: correlation analysis via substituent constants

Кузнецова

Egorochkin

Хамалетдинова

et al. 2016

J. Phys. Org. Chem.

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The elucidation of the mechanism of the substituent influence on the properties P (the interaction energies E, interring distances l, and free energies ΔG of interaction) of weak complexes involving aromatic rings is of importance not only theoretically but also from a practical standpoint. This mechanism is little understood. In this work, the literature data on the substituent influence on P properties for 42 series of complexes have been analyzed, using correlation analysis. Generally, the inductive, resonance, polarizability, and steric effects are in operation. The presence or absence of certain effects and the relation between their contributions are determined by the type of series. The polarizability effect (an electrostatic ion‐dipole interaction) is caused by an excess charge appearing on the ring substituted fragment of complexes as a result of the complexation. This effect is observed in all series; its contribution ranges up to approximately 50%.

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Reactivity and Thermal Stability of Hexafluorides

Cited by 23 publications

References 2 publications

Bond dissociation energies in organometallic systems: substituent effects

Bond dissociation energies in organometallic systems: substituent effects

A Relativistic Density Functional Study on the Uranium Hexafluoride and Plutonium Hexafluoride Monomer and Dimer Species

Noncovalent interactions involving aromatic rings: correlation analysis via substituent constants

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