Intriguing gold trifluoride-molecular structure of monomers and dimers: An electron diffraction and quantum chemical study

Balázs Réffy, M. Kolonits, Axel Schulz, Thomas M. Klapötke, M. Hargittai

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Abstract

The molecular geometry of monomeric and dimeric gold trifluoride, AuF3 and Au2F6, has been determined by gas-phase electron diffraction and high- level quantum chemical calculations. Both experiment and computation indicate that the ground-state structure of AuF3 has C(2v) symmetry, rather than 3- fold symmetry, with one shorter and two longer Au-F bonds and an almost T- shaped form, due to a first-order Jahn-Teller effect. CASSCF calculations show the triplet D(3h) symmetry structure, 3A', to lie about 42 kcal/mol above the 1A1 symmetry ground state and the D(3h) symmetry singlet, 1A', even higher than the triplet state, by about a further 13 kcal/mol. The molecule has a typical 'Mexican-hat'-type potential energy surface with three equal minimum-energy structures around the brim of the hat, separated by equal-height transition structures, about 3.6 kcal/mol above the minimum energy. The geometry of the transition structure has also been calculated. The dimer has a D(2h) symmetry planar, halogen-bridged geometry, with the gold atom having an approximately square-planar coordination, typical for d8 transition metals. The geometries of AuF and Au2F2 have also been calculated. The very short Au···Au separation in Au2F2 is indicative of the so-called aurophilic interaction. This effect is much less pronounced in Au2F6.

Original languageEnglish
Pages (from-to)3127-3134
Number of pages8
JournalJournal of the American Chemical Society
Volume122
Issue number13
DOIs
Publication statusPublished - Apr 5 2000

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Molecular Structure
Electron diffraction
Gold
Dimers
Molecular structure
Monomers
Electrons
Halogens
Geometry
Crystal symmetry
Ground state
Gases
Metals
Jahn-Teller effect
Potential energy surfaces
Transition metals
Atoms
Molecules
Experiments

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Intriguing gold trifluoride-molecular structure of monomers and dimers : An electron diffraction and quantum chemical study. / Réffy, Balázs; Kolonits, M.; Schulz, Axel; Klapötke, Thomas M.; Hargittai, M.

In: Journal of the American Chemical Society, Vol. 122, No. 13, 05.04.2000, p. 3127-3134.

Research output: Contribution to journalArticle

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