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Intriguing Gold TrifluorideMolecular Structure of Monomers and Dimers: An Electron Diffraction and Quantum Chemical Study

Authors :
Mária Kolonits
Magdolna Hargittai
Balázs Réffy
Thomas M. Klapötke
Axel Schulz
Source :
Journal of the American Chemical Society. 122:3127-3134
Publication Year :
2000
Publisher :
American Chemical Society (ACS), 2000.

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 C2v 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 D3h symmetry structure, 3A‘, to lie about 42 kcal/mol above the 1A1 symmetry ground state and the D3h 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 D2h symmetry planar, halogen-bridged geometry, w...

Details

ISSN :
15205126 and 00027863
Volume :
122
Database :
OpenAIRE
Journal :
Journal of the American Chemical Society
Accession number :
edsair.doi...........54350c90efd80e5be9d9fa4c6bca9d65