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Gallium isopropoxide: Synthesis, properties, “coordination polymerism”. New pentanuclear gallium oxoisopropoxochloride

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Abstract

Conditions for the synthesis of gallium isopropoxide (I) by anodic dissolution of the metal in i-PrOH (in the presence of Bu4NBr supporting electrolyte) and by exchange reaction of GaCl3 with i-PrONa were studied. In the latter case, the crude product was a waxy substance (II) infinitely soluble in the alcohol and hydrocarbons and containing 12–30% Cl, which cannot be removed by adding an excess of i-PrONa due to the formation of insoluble NaGa(OPr-i)4. During 1.5–2 months, II is solidified to give non-melting nonvolatile amorphous product (III) poorly soluble in the alcohol. Upon heat treatment of II in vacuum, compound I is distilled off as an oily liquid consisting, according to mass spectrometry, of [Ga(OPr-i)3]2 dimer molecules. It can be retained for a long period of time in the presence of the [Ga(OPr-i)3]4 tetramer crystals. The existence of oligomeric molecules of different size up to polymers (“coordination polymerism”) in the materials is related to the possibility of tetrahedral or octahedral coordination of the metal atom. From concentrated solutions of components, the oxoalkoxochloride [Ga5(µ5-O)(µ-OPr-i)8Cl5] (IV) is crystallized. Its molecule is a flattened tetragonal pyramid. The equatorial plane formed by four gallium atoms has the µ5-O group at the center. The axial Ga atom has an octahedral coordination. All eight sides of the pyramid are drawn together by the µ-OPr-i groups, and the chlorine atoms occupy the terminal positions. (CIF file CCDC no. 693282.)

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Authors and Affiliations

  1. Lomonosov Moscow State University, Moscow, 119991, Russia

    E. V. Suslova, N. Ya. Turova & A. V. Kepman

  2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow, GSP-1, 117813, Russia

    Z. A. Starikova

Authors
  1. E. V. Suslova
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  2. N. Ya. Turova
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  3. Z. A. Starikova
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  4. A. V. Kepman
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Correspondence to E. V. Suslova.

Additional information

Original Russian Text © E.V. Suslova, N.Ya. Turova, Z.A. Starikova, A.V. Kepman, 2016, published in Koordinatsionnaya Khimiya, 2016, Vol. 42, No. 1, pp. 21–28.

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Suslova, E.V., Turova, N.Y., Starikova, Z.A. et al. Gallium isopropoxide: Synthesis, properties, “coordination polymerism”. New pentanuclear gallium oxoisopropoxochloride. Russ J Coord Chem 42, 19–26 (2016). https://doi.org/10.1134/S1070328416010061

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  • DOI: https://doi.org/10.1134/S1070328416010061

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