Ab initio studies of molecular structures and energetics. 4. Hexacoordinated NF6- and CF62- anions

Ewig, Carl S.; Wazer, John R. Van

doi:10.1021/ja00157a017

Cited by 56 publications

(31 citation statements)

References 2 publications

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“…The I4 / m and P4 / n phases are also ionic, but apart from the NF 4 + and/or F − ions they both contain the NF 6 − anion in which pentavalent nitrogen is bonded to six fluorine atoms. This anion was first proposed by Ewig and Van Wazer11 who found it to be dynamically stable in the gas phase, and indeed thermodynamically more stable than NF 5 + F − . To our best knowledge there have been no prior reports on the stabilization of NF 6 − in the solid state.…”

Section: Resultsmentioning

confidence: 78%

“…Theoretical investigations into the properties of the nitrogen pentafluoride molecule (NF 5 ) in the gas phase910111213 indicate that although it is a minimum on the potential energy surface (PES)111213, its decomposition into NF 3 and F 2 is highly exothermic (+1.82 eV per NF 5 )1213. Regarding the geometry of the molecule, the ground state structure of NF 5 is a trigonal bipyramid with five covalent N–F bonds.…”

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confidence: 99%

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Hexacoordinated nitrogen(V) stabilized by high pressure

Kurzydłowski

Zaleski‐Ejgierd

2016

Sci Rep

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In all of its known connections nitrogen retains a valence shell electron count of eight therefore satisfying the golden rule of chemistry - the octet rule. Despite the diversity of nitrogen chemistry (with oxidation states ranging from + 5 to −3), and despite numerous efforts, compounds containing nitrogen with a higher electron count (hypervalent nitrogen) remain elusive and are yet to be synthesized. One possible route leading to nitrogen’s hypervalency is the formation of a chemical moiety containing pentavalent nitrogen atoms coordinated by more than four substituents. Here, we present theoretical evidence that a salt containing hexacoordinated nitrogen(V), in the form of an NF6− anion, could be synthesized at a modest pressure of 40 GPa (=400 kbar) via spontaneous oxidation of NF3 by F2. Our results indicate that the synthesis of a new class of compounds containing hypervalent nitrogen is within reach of current high-pressure experimental techniques.

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Section: Resultsmentioning

confidence: 78%

mentioning

confidence: 99%

Hexacoordinated nitrogen(V) stabilized by high pressure

Kurzydłowski

Zaleski‐Ejgierd

2016

Sci Rep

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“…If so, the so called "experimental force fields"' 5 8 ' 5 9 for these anions should be revised. 11 The orbital energies of the tig-HOMO are positive for AIF6 3 -and GaF 6 3 -and therefore both these anions are certainly electronically unstable, because, according to our experience, when electron relaxation and electron correlation are taken into account the electronic stability of multiply charged anions decreases. InF 6 3 -and TIF 6 3 -both have negative orbital energies of the tig-HOMO: -0.41 eV and -0.20 eV, respectively.…”

Section: Amentioning

confidence: 67%

Vertical Electron Detachment Energies for Octahedral Closed-Shell Multiply-Charged Anions

Gutowski¹,

Boldyrev²,

Ortiz³

et al. 1994

J. Am. Chem. Soc.

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“…There are, however, a number of systems of comparable size which recently have been predicted to form electronically stable free dianions. Apart from the carbon cluster dianions C n 2Ϫ (nϭ7 -10), 2,10,11 these systems typically consist of a central ͑metal͒ atom and three to eight fluorine or chlorine ligands, such as the MX 3 2Ϫ ͑MϭLi, Na, K, XϭF, Cl͒, 8 the MX 4 2Ϫ ͑MϭBe, Mg, Ca, XϭF, Cl͒, 12 the MF 6 2Ϫ ͑MϭC, Si, Cr, Mo, Au, Pt͒, [13][14][15] and the MF 8 2Ϫ ͑MϭTe, Se͒ ͑Ref. 16͒ family.…”

Section: Introductionmentioning

confidence: 99%

A new class of free stable doubly negative systems: First investigations on the SimO2−n series

Sommerfeld¹,

Scheller²,

Cederbaum³

1995

The Journal of Chemical Physics

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Studies on several isomers of the C 2 O n 2Ϫ and Si 2 O n 2Ϫ series of dianionic systems are performed at the Hartree-Fock, configuration interaction, Mo "ller-Plesset perturbation theory and outer-valence Green's function levels of theory. All examined C 2 O n 2Ϫ systems are predicted to be unstable with respect to electron autodetachment. However, the analogues silicon systems Si 2 O n 2Ϫ turn out to be electronically more stable than the corresponding carbon species. For Si 2 O 4 2Ϫ which marks the onset of electronic stability in the Si m O n 2Ϫ series the influence of the basis set and electron correlation on the geometrical parameters as well as on the electron detachment energy are studied in some detail. The possibility of decomposition via fragmentation or adiabatic electron loss is discussed. A simple criterion to determine whether a given structure may represent a promising candidate for a stable dianion of the Si m O n 2Ϫ type is suggested.

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Ab initio studies of molecular structures and energetics. 4. Hexacoordinated NF6- and CF62- anions

Cited by 56 publications

References 2 publications

Hexacoordinated nitrogen(V) stabilized by high pressure

Hexacoordinated nitrogen(V) stabilized by high pressure

Vertical Electron Detachment Energies for Octahedral Closed-Shell Multiply-Charged Anions

A new class of free stable doubly negative systems: First investigations on the SimO2−n series

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