Matrix reactions of alkali metal fluoride molecules with fluorine. Infrared and Raman spectra of the trifluoride ion in the M+F3- species

Ault, Bruce S.; Andrews, Lester

doi:10.1021/ja00422a058

Cited by 87 publications

(59 citation statements)

References 6 publications

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“…Despite some criticism of the term and concept of hypervalency, hypervalent species of the second-row elements 22–24 and hypervalent all-hydrido species 25, 26 have rarely been observed experimentally. We produced hydrogen fluoride anions in an argon matrix by electron bombardment of excess Ar containing a small proportion of methyl fluoride during matrix deposition.…”

Section: Resultsmentioning

confidence: 99%

Identification of a Simplest Hypervalent Hydrogen Fluoride Anion in Solid Argon

Liu

Chen

Chin

et al. 2017

Sci Rep

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Hypervalent molecules are one of the exceptions to the octet rule. Bonding in most hypervalent molecules is well rationalized by the Rundle–Pimentel model (three-center four-electron bond), and high ionic bonding between the ligands and the central atom is essential for stabilizing hypervalent molecules. Here, we produced one of the simplest hypervalent anions, HF−, which is known to deviate from the Rundle–Pimentel model, and identified its ro-vibrational features. High-level ab inito calculations reveal that its bond dissociation energy is comparable to that of dihalides, as supported by secondary photolysis experiments with irradiation at various wavelengths. The charge distribution analysis suggested that the F atom of HF− is negative and hypervalent and the bonding is more covalent than ionic.

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Section: Resultsmentioning

confidence: 99%

Identification of a Simplest Hypervalent Hydrogen Fluoride Anion in Solid Argon

Liu

Chen

Chin

et al. 2017

Sci Rep

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“…The formation of F 2 and its reaction with F Ϫ may lead to the stabilization of F 3 Ϫ in these experiments. Ault and Andrews 74 have reported the infrared and Raman spectra of that species, trapped in an argon matrix following the reaction between F 2 and an alkali metal fluoride. The anion was found to be linear, with a 3 absorption at 550 cm Ϫ1 .…”

Section: Processes Which Occur In the Matrixmentioning

confidence: 99%

Matrix isolation study of the interaction of excited neon atoms with BF3: Infrared spectra of BF2, BF+2, BF+3, and BF−3

Jacox

Thompson

1995

The Journal of Chemical Physics

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When a Ne:BF3 sample is codeposited at approximately 5 K with a beam of neon atoms that have been excited in a microwave discharge, the infrared spectrum of the resulting solid deposit shows prominent absorptions of BF2. All three vibrational fundamentals and the ν1+ν3 combination band of BF2 isolated in solid neon are identified, and a normal coordinate analysis is conducted. In addition, infrared absorptions of the BF+3, BF+2, and BF−3 molecular ions are assigned, and the processes which occur when the solid deposit is exposed to visible and ultraviolet radiation are considered.

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“…It was found that the discriminating factor is the smaller effective size of H and C compared to the larger Li and Si atoms, and the resulting lack of space around them. Nonetheless, it is to be noted that the valence expanded HF 2 -has been well characterized by the condensed and gas phase experimentalist [386], and even F 3 -has been studied as a gas-phase anion [387] and associated with alkali metal cations, in a cryogenic matrix [388].…”

Section: Issuementioning

confidence: 99%

Interplay of thermochemistry and Structural Chemistry, the journal (volume 18, 2007) and the discipline

Ponikvar

Liebman

2008

Struct Chem

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In this study, we relate the contents of the journal Structural Chemistry for the calendar year 2007 and thermochemistry. The year's articles were briefly summarized and a thermochemical comment written to supplement them. Frequently questions were asked and future research was suggested.Keywords Structural Chemistry Á Thermochemistry Á Thermodynamics Á Enthalpy of formation Á Enthalpy of phase change Á Enthalpy of reaction As practiced disciplines, structural chemistry and thermochemistry are very often unrelated. In this study, these disciplines are linked as relations are explicitly made using the contents of the journal Structural Chemistry (Vol. 18) for the calendar year 2007 as a scaffold for our analysis, for our selected articles in the discipline of structural chemistry. These studies have been reviewed by us, where we give them a thermochemical flavor. While this commentary is most generally written in terms of brief summaries of literature papers involving enthalpies of formation and/or reaction, not uncommonly we raise questions and even suggest possible future research. We are not, however, going to give a thermochemical slant on book reviews, honorary dedications, and obituaries although these works will be cited in our text.As such, this article is a sequel to our earlier related reviews of Structural Chemistry for the calendar years 2000 through 2004 [1-5]. Reviews for 2005 and 2006 are currently being prepared. Issue 1In the first article in the first issue of Structural Chemistry for 2007, Hargittai [6] asserted that while research is currently usually carried out in big groups, the most important ideas, observations and discoveries still belong to individuals who have to bring down dogmas or open entirely new areas in science. This may bring solace to the thermochemical community in which research groups are generally small, and the number of new practitioners sadly few.In the past decade, the crystal engineering of multidimensional arrays and networks containing metal ions has achieved considerable progress because of the increased interest in the potential utility of these compounds as zeolite-like materials [7-11], catalysts [12], or magnetic materials [13][14][15]. The thermochemistry of these species is complicated by their inherent complexity: however, estimation approaches of their key thermochemical quantities are increasingly reliable [16]. In the second article of this issue, by Wang et al. [17], the versatility of malonate dianion as a ligand for the construction of extended networks with different topologies dependent on the coordination geometry of the metal ion was discussed. The synthesis and structure of a novel malonate-bridged copper(II) compound in which copper(II) ions have two different coordination environments in a novel three-dimensional (3D) network was described. Metal malonates have been studied from a

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Matrix reactions of alkali metal fluoride molecules with fluorine. Infrared and Raman spectra of the trifluoride ion in the M+F3- species

Cited by 87 publications

References 6 publications

Identification of a Simplest Hypervalent Hydrogen Fluoride Anion in Solid Argon

Identification of a Simplest Hypervalent Hydrogen Fluoride Anion in Solid Argon

Matrix isolation study of the interaction of excited neon atoms with BF3: Infrared spectra of BF2, BF+2, BF+3, and BF−3

Interplay of thermochemistry and Structural Chemistry, the journal (volume 18, 2007) and the discipline

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