Ab initio study of the isoelectronic series N3−, N2O and N2F+: Predicting the bond lengths in N2F+

Peters, Nancy J. S.

doi:10.1016/0009-2614(87)87253-6

Cited by 6 publications

(3 citation statements)

References 21 publications

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“…The N 2 F + cation has been the subject of various spectroscopic, structural, and theoretical investigations. ,,− ,− The most interesting features are the unusually short N−N and N−F bond lengths of 1.1034(5) and 1.2461(10) Å, respectively, observed by Botschwina et al for the free gaseous ion using millimeter-wave spectroscopy . The shortest experimentally observed N−N bond distance is 1.09277(9) Å in N 2 H + .…”

Section: Resultsmentioning

confidence: 99%

Dinitrogen Difluoride Chemistry. Improved Syntheses ofcis- andtrans-N₂F₂, Synthesis and Characterization of N₂F⁺Sn₂F₉⁻, Ordered Crystal Structure of N₂F⁺Sb₂F₁₁⁻, High-Level Electronic Structure Calculations ofcis-N₂F₂,trans-N₂F₂, F₂N═N, and N₂F⁺, and Mechanism of thetran

Dixon
¹
,

Grant
²
,

Haiges
³

et al. 2010

Inorg. Chem.

27
2
14
2

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N(2)F(+) salts are important precursors in the synthesis of N(5)(+) compounds, and better methods are reported for their larger scale production. A new, marginally stable N(2)F(+) salt, N(2)F(+)Sn(2)F(9)(-), was prepared and characterized. An ordered crystal structure was obtained for N(2)F(+)Sb(2)F(11)(-), resulting in the first observation of individual N[triple bond]N and N-F bond distances for N(2)F(+) in the solid phase. The observed N[triple bond]N and N-F bond distances of 1.089(9) and 1.257(8) A, respectively, are among the shortest experimentally observed N-N and N-F bonds. High-level electronic structure calculations at the CCSD(T) level with correlation-consistent basis sets extrapolated to the complete basis limit show that cis-N(2)F(2) is more stable than trans-N(2)F(2) by 1.4 kcal/mol at 298 K. The calculations also demonstrate that the lowest uncatalyzed pathway for the trans-cis isomerization of N(2)F(2) has a barrier of 60 kcal/mol and involves rotation about the N=N double bond. This barrier is substantially higher than the energy required for the dissociation of N(2)F(2) to N(2) and 2 F. Therefore, some of the N(2)F(2) dissociates before undergoing an uncatalyzed isomerization, with some of the dissociation products probably catalyzing the isomerization. Furthermore, it is shown that the trans-cis isomerization of N(2)F(2) is catalyzed by strong Lewis acids, involves a planar transition state of symmetry C(s), and yields a 9:1 equilibrium mixture of cis-N(2)F(2) and trans-N(2)F(2). Explanations are given for the increased reactivity of cis-N(2)F(2) with Lewis acids and the exclusive formation of cis-N(2)F(2) in the reaction of N(2)F(+) with F(-). The geometry and vibrational frequencies of the F(2)N=N isomer have also been calculated and imply strong contributions from ionic N(2)F(+) F(-) resonance structures, similar to those in F(3)NO and FNO.

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Section: Resultsmentioning
confidence: 99%

Dinitrogen Difluoride Chemistry. Improved Syntheses ofcis- andtrans-N₂F₂, Synthesis and Characterization of N₂F⁺Sn₂F₉⁻, Ordered Crystal Structure of N₂F⁺Sb₂F₁₁⁻, High-Level Electronic Structure Calculations ofcis-N₂F₂,trans-N₂F₂, F₂N═N, and N₂F⁺, and Mechanism of thetran
Dixon
¹
,
Grant
²
,
Haiges
³

et al. 2010
Inorg. Chem.
27
2
14
2
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“…It has been used as a precursor of N 5 + salts and as an electrophilic fluorinating agent . The theoretical studies of this cation have been limited to the characterization of its bonding. − …”

Section: Introductionmentioning
confidence: 99%

Theoretical Study of Complexes and Fluoride Cation Transfer between N₂F⁺and Electron Donors
Alkorta
¹
,
Solimannejad
²
,
Provasi
³

et al. 2007
J. Phys. Chem. A
53
14
19
0
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A theoretical study of the complexes formed by the N 2 F cation (fluorodiazonium ion) and a series of small molecules containing nitrogen atoms have been carried out at the MP2 computational level. In addition, fluorine transfer has been studied. The electron density, NMR shielding and indirect coupling constants of the complexes have been evaluated. The covalent or halogen bonding characteristics of the N‚‚‚F interactions observed in the complexes are defined by the interatomic distance. It has been determined that the limiting value is 1.6 Å.

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“…The first ab initio study on N 2 F + was reported in 1975 by Pulay et al 5 who performed Hartree−Fock calculations to predict the r N−F = 1.28 Å and r N−N = 1.10 Å bond distances and also the vibrational force constants. In 1978, Peters 6 employed the MP2/6-31G* method to find r N−F = 1.256 Å, r N−N = 1.138 Å and a heat of formation ΔH f 0 = 329 kcal/mol. The first crystallographic study of N 2 F + AsF 6 − salt was carried out in 1991 by Christe et al 7 They found a total r N−F + r N−N = 2.316 Å distance which was empirically partitioned as r N−F = 1.217 Å and r N−N = 1.099 Å.…”

Section: Introductionmentioning
confidence: 99%

Theoretical ab Initio Study of the Series of N₂X⁺ Cations with X = F, Cl, Br, and I. New Insights on the “Unusual” N₂F⁺ Species
Papakondylis
¹

2016
J. Phys. Chem. A
4
0
1
0
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The series of cations NX(X̃Σ), with X = F, Cl, Br, I, has been theoretically studied by variational multireference CI and coupled-cluster techniques in conjunction with basis sets of quintuple-ζ quality. We report electronic and geometric structure data and harmonic frequencies as well as binding energies and potential energy curves. A new rationalization is provided for the bonding mode in NF, which provides an explanation for the unusually short N-F bond.

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Ab initio study of the isoelectronic series N3−, N2O and N2F+: Predicting the bond lengths in N2F+

Cited by 6 publications

References 21 publications

Theoretical Study of Complexes and Fluoride Cation Transfer between N₂F⁺and Electron Donors

Theoretical ab Initio Study of the Series of N₂X⁺ Cations with X = F, Cl, Br, and I. New Insights on the “Unusual” N₂F⁺ Species

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Ab initio study of the isoelectronic series N3−, N2O and N2F+: Predicting the bond lengths in N2F+

Cited by 6 publications

References 21 publications

Dinitrogen Difluoride Chemistry. Improved Syntheses ofcis- andtrans-N2F2, Synthesis and Characterization of N2F+Sn2F9−, Ordered Crystal Structure of N2F+Sb2F11−, High-Level Electronic Structure Calculations ofcis-N2F2,trans-N2F2, F2N═N, and N2F+, and Mechanism of thetran

Dinitrogen Difluoride Chemistry. Improved Syntheses ofcis- andtrans-N2F2, Synthesis and Characterization of N2F+Sn2F9−, Ordered Crystal Structure of N2F+Sb2F11−, High-Level Electronic Structure Calculations ofcis-N2F2,trans-N2F2, F2N═N, and N2F+, and Mechanism of thetran

Theoretical Study of Complexes and Fluoride Cation Transfer between N2F+and Electron Donors

Theoretical ab Initio Study of the Series of N2X+ Cations with X = F, Cl, Br, and I. New Insights on the “Unusual” N2F+ Species

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Theoretical Study of Complexes and Fluoride Cation Transfer between N₂F⁺and Electron Donors

Theoretical ab Initio Study of the Series of N₂X⁺ Cations with X = F, Cl, Br, and I. New Insights on the “Unusual” N₂F⁺ Species