Structure and energy studies of β-diketonates. XIII. Molecular structure of gadolinium tris-hexafluoroacetylacetonate Gd(C5O2HF6)3 |
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Authors: | G. V. Girichev N. V. Tverdova S. A. Shlykov V. V. Rybkin N. P. Kuzmina A. Yu. Rogachev |
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Affiliation: | (1) Ivanovo State Chemical Technological University, Russia;(2) M. V. Lomonosov Moscow State University, Russia |
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Abstract: | In a mass spectrometric study, it was found that the saturated vapor over gadolinium tris-hexafluoroacetylacetonate Gd(C5O2HF6)3 contains molecular forms with a mass exceeding the mass of the dimer. The vapor overheated to 250–300°C contains only the monomer form. Simultaneous electron diffraction and mass spectrometric experiment aimed at investigating the structure of the Gd(hfa)3 monomer molecule was carried out at 284(5)°C. The Gd(hfa)3 molecule was found to have the symmetry of the equilibrium D 3 configuration. The basic structural parameters are r h1(Gd-O) = 2.291(10) Å, r h1(O-C) = 1.257(10) Å, r h1(C-Cr) = 1.404(6) Å, r h1(CF-F)av = 1.341(3) Å, ∠OGdO = 72.8(0.4)°. The GdO6 coordination polyhedron has the structure of a distorted antiprism. The rotation angle of the O-O-O trigonal faces relative to their position in a regular prism is 18.7(0.9)°. Quantum chemical calculations (HF/SBK, 6-31G*) generally reproduce the experimental structure, but the Gd-O internuclear distance is exaggerated by 0.04 Å. |
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Keywords: | gas-phase electron diffraction mass spectrometry quantum chemistry metal β -diketonates molecular structure |
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