New calсium β-diketonate complexes: The monomeric complexes [Ca(PhCOCHCOCF 3) 2(15-crown-5)], [Ca(AdCOCHCOCF 3) 2(15-crown-5)] and the binuclear hydrated complex [{Ca(adtfa)(18-crown-6)(H 2O)}{Ca(adtfa) 3(H 2O)}(EtOH)]. Synthesis, characterization and crystal structure

The new monomeric complexes [Ca(PhCOCHCOCF 3) 2(15-crown-5)], [Ca(AdCOCHCOCF 3) 2(15-crown-5)] and the binuclear hydrated complex [Ca 2(AdCOCHCOCF 3) 4(18-crown-6)(H 2O)(C 2H 5OH)] have been prepared. The all complexes were characterized by NMR-spectroscopy, single-crystal X-ray diffraction methods,...

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Published inPolyhedron Vol. 30; no. 12; pp. 1945 - 1952
Main Authors Pochekutova, Tatjana S., Khamylov, Vyacheslav K., Fukin, Georgy K., Kurskii, Yury A., Petrov, Boris I., Shavyrin, Andrey S., Arapova, Alla V.
Format Journal Article
LanguageEnglish
Published Elsevier Ltd 01.08.2011
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Summary:The new monomeric complexes [Ca(PhCOCHCOCF 3) 2(15-crown-5)], [Ca(AdCOCHCOCF 3) 2(15-crown-5)] and the binuclear hydrated complex [Ca 2(AdCOCHCOCF 3) 4(18-crown-6)(H 2O)(C 2H 5OH)] have been prepared. The all complexes were characterized by NMR-spectroscopy, single-crystal X-ray diffraction methods, DSC and TGA. [Display omitted] ► Synthesis of the novel monomeric [Ca(btfa) 2(15-crown-5)], [Ca(adtfa) 2(15-crown-5)](C 6H 5CH 3) 0.5. ► Synthesis of the ion-paired solvated adduct [Ca 2(adtfa) 4](18-crown-6)](H 2O) 2(C 2H 5OH). ► Characterization of compounds by elemental analyses, IR-spectroscopy, NMR-spectroscopy, single-crystal X-ray diffraction methods, DSC and TGA methods. The preparation of the Ca-β-diketonate complexes with crown-ethers, [Ca(btfa) 2(15-crown-5)] ( 1), [Ca(adtfa) 2(15-crown-5)] ( 2), [Ca(adtfa) 2(15-crown-5)](C 6H 5CH 3) 0.5 ( 3) and [{Ca(adtfa)(18-crown-6)(H 2O)}{Ca(adtfa) 3(H 2O)}(EtOH)] ( 4) (btfa = 1,1,1-trifluoro-4-phenyl-butanedionato-2,4; adtfa = 1,1,1-trifluoro-4-(1-adamantyl)butanedionato-2,4; 15-crown-5 = 1,4,7,10,13-pentaoxacyclopentadecane; 18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane), is described. Complex 1 has been prepared from the reaction of metallic Ca with 2 eq. of Hbtfa and 1 eq. of 15-crown-5 in toluene; complex 2 has been prepared from the reaction of metallic Ca with 2 eq. of Hadtfa and 1 eq. of 15-crown-5 in ethanol. The solvated complex 3 was obtained by cooling of a toluene–hexane solution of 2. The hydrated complex 4 was prepared from the reaction of metallic Ca with 2 eq. of Hadtfa and 1 eq. of 18-crown-6, followed by addition of excess H 2O to the resulting reaction mixture. The all complexes were characterized by elemental analyses, IR-spectroscopy, NMR-spectroscopy, single-crystal X-ray diffraction methods, DSC and TGA. A single-crystal X-ray study of 1 and 3 has show that complexes 1 and 3 are monomeric and contain the calcium atom bonded with two β-diketonate ligands and one molecule of crown-ether. Complex 4, as shown by X-ray analyses, is an ion-paired solvated adduct, containing the cation {Ca(adtfa)(18-crown-6)(H 2O)} + and the anion {Ca(adtfa) 3(H 2O)} −. The monomeric complexes 1– 3 are volatile and thermally stable in the temperature range 100–260 °C. Complex 4 undergoes decomposition above 110 °C with consecutive loss of ethanol, H 2O, 18-crown-6 and some evaporization of 4.
ISSN:0277-5387
DOI:10.1016/j.poly.2011.04.046