Thermochemistry of alkali metal hexafluoromolybdates(V) and hexafluorotungstates(V)

Burgess, John; Haigh, I.; Peacock, R. D.; Taylor, Paul

doi:10.1039/dt9740001064

Cited by 24 publications

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“…The high electron binding energy in the corresponding negative ions MX k +1 - when compared to those for X - is due to delocalization of the additional electron over k +1 X groups, as opposed to a single X. The EAs of many superhalogens have been estimated both theoretically − and experimentally. − However, direct measurements of the high electron binding energies in the MX k +1 - superhalogens were not possible until recently.…”

Section: Introductionmentioning

confidence: 99%

MX₃^- Superhalogens (M = Be, Mg, Ca; X = Cl, Br): A Photoelectron Spectroscopic and ab Initio Theoretical Study

et al. 2005

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Gas-phase alkaline earth halide anions, MgX3(-) and CaX3(-) (X = Cl, Br), were produced using electrospray and investigated using photoelectron spectroscopy at 157 nm. Extremely high electron binding energies were observed for all species and their first vertical detachment energies were measured as 6.60 +/- 0.04 eV for MgCl3(-), 6.00 +/- 0.04 eV for MgBr3(-), 6.62 +/- 0.04 eV for CaCl3(-), and 6.10 +/- 0.04 eV for CaBr3(-). The high electron binding energies indicate these are very stable anions and they belong to a class of anions, called superhalogens. Theoretical calculations at several levels of theory were carried out on these species, as well as the analogous BeX3(-). Vertical detachment energy spectra were predicted to compare with the experimental observations, and good agreement was obtained for all species. The first adiabatic detachment energies were found to be substantially lower (by about 1 eV) than the corresponding vertical detachment energies for all the MX3(-) species, indicating extremely large geometry changes between MX3(-) and MX3. We found that all the MX3(-) anions possess D3h ((1)A1') structures and are extremely stable against dissociation into MX2 and X-. The corresponding neutral species MX3, however, were found to be only weakly bound with respect to dissociation toward MX2 + X. The global minimum structures of all the MX3 neutrals were found to be C2v ((2)B2), which can be described as (X2(-))(MX+) charge-transfer complexes, whereas the MX2...X (C2v, (2)B1) van der Waals complexes were shown to be low-lying isomers.

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Section: Introductionmentioning

confidence: 99%

MX₃^- Superhalogens (M = Be, Mg, Ca; X = Cl, Br): A Photoelectron Spectroscopic and ab Initio Theoretical Study

et al. 2005

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“…E°for the MoF6/MoF6" couple occurs at a much more positive potential and hence MoF6 is shown to be the stronger oxidant of the two, which is in agreement with the findings of the earlier chemical studies6-8 and with recent estimates of the electron affinities for the two hexafluorides. 24 The observed difference of E°of 1 V for the reduction of MoF6 and WF6 is much greater than had been anticipated, particularly when aqueous systems are considered. It provides quantitative evidence that MoF6 is a much stronger oxidant than WF6 in fluoride media.…”

Section: Moof4mentioning

confidence: 84%

Electrochemical studies of molybdenum hexafluoride and related compounds in anhydrous hydrogen fluoride

Bond¹,

IRVINE²,

O’Donnell³

1977

Inorg. Chem.

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The Theoretical Investigation of the Electron Affinity of Chemical Compounds

Gutsev¹,

Boldyrev

1985

Advances in Chemical Physics

119

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Thermochemistry of alkali metal hexafluoromolybdates(V) and hexafluorotungstates(V)

Cited by 24 publications

References 0 publications

MX₃^- Superhalogens (M = Be, Mg, Ca; X = Cl, Br): A Photoelectron Spectroscopic and ab Initio Theoretical Study

MX₃^- Superhalogens (M = Be, Mg, Ca; X = Cl, Br): A Photoelectron Spectroscopic and ab Initio Theoretical Study

Electrochemical studies of molybdenum hexafluoride and related compounds in anhydrous hydrogen fluoride

The Theoretical Investigation of the Electron Affinity of Chemical Compounds

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Thermochemistry of alkali metal hexafluoromolybdates(V) and hexafluorotungstates(V)

Cited by 24 publications

References 0 publications

MX3- Superhalogens (M = Be, Mg, Ca; X = Cl, Br): A Photoelectron Spectroscopic and ab Initio Theoretical Study

MX3- Superhalogens (M = Be, Mg, Ca; X = Cl, Br): A Photoelectron Spectroscopic and ab Initio Theoretical Study

Electrochemical studies of molybdenum hexafluoride and related compounds in anhydrous hydrogen fluoride

The Theoretical Investigation of the Electron Affinity of Chemical Compounds

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Product

Resources

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MX₃^- Superhalogens (M = Be, Mg, Ca; X = Cl, Br): A Photoelectron Spectroscopic and ab Initio Theoretical Study

MX₃^- Superhalogens (M = Be, Mg, Ca; X = Cl, Br): A Photoelectron Spectroscopic and ab Initio Theoretical Study