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STRUCTURE AND THERMAL PROPERTIES OF VOLATILE MIXED-LIGAND MAGNESIUM COMPLEXES: EFFECT OF TERT-BUTYL AND PHENYL SUBSTITUTES IN A FLUORINATED β-DIKETONATE

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Abstract

Structures of volatile mixed-ligand complexes of magnesium with N,N,N′,N′-tetramethylethylenediamine (tmeda) and fluorinated β-diketonate ligands L = CF3C(O)CHC(O)R– (R = t-Bu (ptac) and Ph (btfac)) are determined. Complex [Mg(tmeda)(btfac)2] is obtained for the first time and is characterized by elemental analysis and IR spectrometry. Both [Mg(tmeda)(L)2] compounds are molecular complexes, and the symmetry of their crystals is increased due to the presence of an aromatic substituent: space groups Pccn (L = btfac) and P21/n (L = ptac). The magnesium atom occurs in a distorted octahedral environment of three chelate ligands. The bond lengths and chelate angles in both complexes are similar: d(Mg–N) = 2.226(2)-2.245(1) Å, d(Mg–O) = 2.030(2)-2.043(2) Å, θ(N–Mg–N) = 80.97(7)-81.68(10)°, θ(O–Mg–O) = 85.61(9)-85.75(7)°. The Hirshfeld surfaces (CrystalExplorer, Tonto) show a presence of weak intermolecular contacts C–HPh…F in the [Mg(tmeda)(btfac)2] packing (4 contacts per molecule). The qualitative order of volatility decrease for the complexes and their hexafluoroacetylacetonate analogue [Mg(tmeda)(hfac)2] (TGA and vacuum sublimation data) corresponds to the estimated energy increase of [Mg(tmeda)(L)2] crystal lattices (CrystalExplorer, B3LYP/6-31G(d,p)): L = hfac ~ ptac >> btfac.

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Funding

The work was funded by the Russian Science Foundation (project 21-73-00252).

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Authors and Affiliations

  1. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia

    E. S. Vikulova, A. S. Sukhikh, M. A. Mikhaylova, A. A. Nazarova, K. V. Zherikova & N. B. Morozova

  2. Novosibirsk State University, Novosibirsk, Russia

    A. S. Sukhikh & M. A. Mikhaylova

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  1. E. S. Vikulova
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Russian Text © The Author(s), 2022, published in Zhurnal Strukturnoi Khimii, 2022, Vol. 63, No. 8, 97037.https://doi.org/10.26902/JSC_id97037

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Vikulova, E.S., Sukhikh, A.S., Mikhaylova, M.A. et al. STRUCTURE AND THERMAL PROPERTIES OF VOLATILE MIXED-LIGAND MAGNESIUM COMPLEXES: EFFECT OF TERT-BUTYL AND PHENYL SUBSTITUTES IN A FLUORINATED β-DIKETONATE. J Struct Chem 63, 1323–1332 (2022). https://doi.org/10.1134/S0022476622080133

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