The First Direct Observation of the Trifluoride Anion (F<sub>3</sub><sup>-</sup>) in the Gas Phase

Tuinman, Albert A.; Gakh, Andrei A.; Hinde, Robert J.; Compton, R. N.

doi:10.1021/ja991757x

Cited by 47 publications

(52 citation statements)

References 33 publications

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“…They also predicted that the third mode, with b 2 symmetry, shows almost no IR intensity, which explains why Howard and Andrews were unable to observe it. The free [F 2 ] − anion has, thus far, only been observed in mass‐spectrometric experiments . Table shows the IR, Raman, and calculated vibrational bands for the difluorine monoanion.…”

Section: Polyfluorine Anionsmentioning

confidence: 99%

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

et al. 2020

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This Review deals with the evolving field of polyhalogen chemistry, specifically polyhalogen anions (polyhalides). In addition to a historical outline, current progress in synthetic approaches towards the formation of polyfluorides, polychlorides, polybromides, and polyinterhalides is also illustrated. The structural diversity of polyhalides has substantially increased in the past decade, especially for polychlorides and polybromides, which are commonly characterized by single‐crystal X‐ray diffraction, Raman spectroscopy, and quantum‐chemical calculations. Polyfluorides have been examined by sophisticated state‐of‐the‐art quantum‐chemical calculations and investigated spectroscopically in noble gas matrix‐isolation experiments under cryogenic conditions at 4 K. The bonding in such polyhalide systems is also discussed. The last Section deals with applications of polyhalides in halogenation reactions and electrochemistry as well as their use as reactive ionic liquids, emphasizing the promising future of polyhalogen chemistry.

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Section: Polyfluorine Anionsmentioning

confidence: 99%

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

et al. 2020

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“…Only the F 3 − anion is shown on a diagram displaying all experimentally observed polyhalide anions in a recent review by Haller and Riedel. 1 This anion had attracted a lot of attention from theoreticians 22−31 before having been observed by Compton et al, 32 although exhaustive attempts to synthesize a [N(CH 3 ) 4 ] + F 3 − salt were unsuccessful. 33 According to the results of computations, the F 3 − anion possesses a strong multireference 34 character and a fourelectron three-center (4e, 3c) bond.…”

Section: Introductionmentioning

confidence: 99%

Structure and Properties of Polyfluoride F_n^–Clusters (n= 3–29)

et al. 2015

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The electronic and geometrical structures of the neutral Fn and singly negatively charged Fn(-) polyfluorides (n = 3-29) are studied using three levels of theory: density functional theory (DFT) with generalized gradient approximation, hybrid Hartree-Fock-DFT, and hybrid HF-DFT with long-range corrections. For n > 4, each polyfluoride possesses a number of states with different geometries that are closely spaced in total energy. The geometrical structures of the lowest total energy states follow different patterns for the even-n and odd-n Fn(-) anion branches with a preference for higher symmetry geometries. The largest F29(-) anion considered is found to possess Oh symmetry. All the anions beginning with F3(-) are found to possess adiabatic and vertical electron detachment energies exceeding the electron affinities of halogen atoms and are therefore superhalogen anions. Electron affinities, energies of formation, and binding energies show oscillatory behavior as functions of the number n of fluorine atoms. The neutral Fn species are found to be barely stable and are bound by polarization forces. The Fn(-) anions, on the contrary, are quite stable toward the loss of F, F(-), and F2(-), but not to the loss of F2.

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“…Gleichzeitig ergaben sie, dass die dritte Mode mit b 2 ‐Symmetrie so gut wie keine IR‐Intensität aufweist, was erklärt, warum Howard und Andrews diese nicht beobachteten. Freie [F 2 ] − ‐Anionen konnten bisher nur mittels Massenspektrometrie beobachtet werden . Tabelle zeigt experimentelle und berechnete IR‐ und Raman‐Daten für das Difluorid.…”

Section: Polyfluorideunclassified

“…110 kJ mol −1 passt . Seitdem wurden zahlreiche weitere quantenchemische Untersuchungen publiziert . 2010 fand man heraus, dass unter Tieftemperaturbedingungen das freie Trifluorid bei gleichzeitiger Abscheidung von laserablatierten Übergangsmetallen mit Fluor gebildet wird.…”

Section: Polyfluorideunclassified

Polyhalogen‐ und Polyinterhalogen‐Anionen von Fluor bis Iod

et al. 2020

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Dieser Aufsatz widmet sich dem wachsenden Gebiet der Polyhalogen‐Chemie und insbesondere den Polyhalogen‐Anionen (Polyhalogenide). Neben einem historischen Abriss werden aktuelle Entwicklungen in der Synthese von Polyfluoriden, ‐chloriden, ‐bromiden und ‐interhalogeniden erläutert. Die Strukturvielfalt der Polyhalogenide hat in den letzten zehn Jahren drastisch zugenommen, besonders für Polychloride und ‐bromide, die gewöhnlich mittels Einkristallröntgenbeugung, Raman‐Spektroskopie sowie quantenchemischer Rechnungen charakterisiert werden. Polyfluoride wurden sowohl mit modernsten quantenchemischen Methoden als auch mittels spektroskopischer Verfahren in Edelgas‐Matrixisolationsexperimenten bei 4 K untersucht. Die Bindungssituation in Polyhalogeniden wird diskutiert, und der letzte Abschnitt dieses Aufsatzes widmet sich der Anwendung von Polyhalogeniden in Halogenierungsreaktionen und der Elektrochemie sowie als reaktive ionische Flüssigkeiten und zeigt vielversprechende Perspektiven für die Zukunft des Gebiets der Polyhalogen‐Chemie auf.

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The First Direct Observation of the Trifluoride Anion (F₃^-) in the Gas Phase

Cited by 47 publications

References 33 publications

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

Structure and Properties of Polyfluoride F_n^–Clusters (n= 3–29)

Polyhalogen‐ und Polyinterhalogen‐Anionen von Fluor bis Iod

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The First Direct Observation of the Trifluoride Anion (F3-) in the Gas Phase

Cited by 47 publications

References 33 publications

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine

Structure and Properties of Polyfluoride Fn–Clusters (n= 3–29)

Polyhalogen‐ und Polyinterhalogen‐Anionen von Fluor bis Iod

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The First Direct Observation of the Trifluoride Anion (F₃^-) in the Gas Phase

Structure and Properties of Polyfluoride F_n^–Clusters (n= 3–29)