Formation of a solvate of manganese(III) acetylacetonate with chloroform
Metal acetylacetonates are coordination compounds consisting of the acetylacetonate anion (CH3COCHCOCH3, indicated as acac) and metal ions. Typically, both oxygen atoms of the anion bind with the metal and form a six-membered chelate ring. The simplest complexes have the formulas M(acac)3 and M(acac)2. Many complexes are soluble in organic solvents, and such solutions are used for the synthesis of catalysts. The processes of formation of solvates of acetylacetonates of various metals have not been studied properly. It should be noted that the determination of the composition and properties of solvates is important for understanding the peculiarities of the extraction processes of metal acetylacetonates.
Manganese(III) acetylacetonate Mn(acac)3, for example, is also widely used. The recrystallisation of the complex is most commonly conducted from solutions in chloroform, and in this case, the corresponding solvates may be formed, which can affect the structure and properties of Mn(acac)3. There are no data on the synthesis conditions and the composition of the solvates of manganese(III) acetylacetonate with chloroform. Therefore, the purpose of this work is to study the possibilities of its formation and to establish the composition of such solvates.
The formation of the solvate in solution was established using Fourier IR spectroscopy by the shift of the absorption band of the C-H chloroform bond. The composition of the Mn(acac)3· 2CHCl3 solvate was determined using gravimetric analysis.
Sleightholme A. E. S., Shinkle A. A., Liu Q., Li Y., Monroe C. W., Thompson L. T. Non-aqueous manganese acetylacetonate electrolyte for redox flow batteries. Journal of Power Sources. 2011;196(13): 5742–5745. https://doi.org/10.1016/j.jpowsour.2011.02.020
Hirano M., Yakabe S., Clark J. H., Morimoto T. Synthesis of sulfoxides by the oxidation of sulfides with sodium chlorite catalysed by manganese(III) acetylacetonate in acetone in the presence of alumina. Journal of the Chemical Society, Perkin Transactions 1. 1996;22: 2693–2698. https://doi.org/10.1039/P19960002693
Dewar M. J. S., Nakaya T. Oxidative coupling of phenols. Journal of the American Chemical Society. 1968;90(25): 7134–7135. https://doi.org/10.1021/ja01027a051
Van Gorkum R., Bouwman E., Reedijk J. Fast Autoxidation of ethyl linoleate catalyzed by [Mn(acac)3] and bipyridine: A possible drying catalyst for alkyd paints. Inorganic Chemistry. 2004;43(8): 2456–2458. https://doi.org/10.1021/ic0354217
Sharma R. K., Yadav M., Monga Y., Gaur R., Adholeya A., Zboril R., Varma R. S., Gawande M. B. Silica-based magnetic manganese nanocatalyst – Applications in the oxidation of organic halides and alcohols. ACS Sustainable Chemistry & Engineering. 2016;4(3): 1123–1130. https://doi.org/10.1021/acssuschemeng.5b01183
Ban H. T., Kase T., Murata M. Manganese-based transition metal complexes as new catalysts for olefin
polymerizations. Journal of Polymer Science, Part A: Polymer Chemistry. 2001;39(21): 3733–3738. https://doi.org/10.1002/pola.10021
Park Y. J., Kim J. G., Kim M. K., Chung H. T., Kim H. G. Preparation of LiMn2O4 thin films by a sol–gel method. Solid State Ionics. 2000;130(3-4): 203–214. https://doi.org/10.1016/S0167-2738(00)00551-8
Shimizu Y., Murata T. Sol–gel synthesis of perovskite-type lanthanum manganite thin films and fine powders using metal acetylacetonate and poly(vinyl alcohol). Journal of the American Ceramic Society. 1997;80(10): 2702–2704. https://doi.org/10.1111/j.1151-2916.1997.tb03178.x
Steinbach J. F., Burns J. H. Chloroform-bearing chelates. Journal of the American Chemical Society. 1958;80(8): 1839–1841. https://doi.org/10.1021/ja01541a018
Clarke F. R., Steinbach J. F., Wagner W. F. Halomethane solvates of tervalent acetylacetonates. Journal of Inorganic and Nuclear Chemistry. 1964;26(7): 1311–1316. https://doi.org/10.1016/0022-1902(64)80215-3
Grinvald I. I., Kalagaev I. Yu., Petukhov A. N., Grushevskaya A. I., Kapustin R. V., Vorotyntsev I. V. Association of haloforms in condensed and gas phases. Ir spectroscopy and Dft calculations. Journal of Structural Chemistry. 2018;59(2): 313–320. https://doi.org/10.1134/S0022476618020087
Pinchas S., Silver B. L., Laulicht I. Infrared absorption spectra of the 18O-labeled acetylacetonates of Cr(III) and Mn(III). Journal of Chemical Physics. 1967; 46(4): 1506–1510. https://doi.org/10.1063/1.1840881
Lawson K. E. The infrared absorption spectra of metal acetylacetonates. Spectrochimica Acta. 1961;17(3): 248–258. https://doi.org/10.1016/0371-1951(61)80071-4
Diaz-Acosta I., Baker J., Hinton J. F., Pulay P. Calculated and experimental geometries and infrared spectra of metal tris-acetylacetonates: vibrational spectroscopy as a probe of molecular structure for ionic complexes. Part II. Spectrochimica Acta, Part A. 2003;59(2): 363-377. https://doi.org/10.1016/S1386-1425(02)00166-X
Copyright (c) 2022 Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases
This work is licensed under a Creative Commons Attribution 4.0 International License.