TY - JOUR

T1 - Study of potassium, rubidium hexafluoroacetylacetonates and by-products of their synthesis and crystallization

AU - Kochelakov, D. V.

AU - Vikulova, E. S.

AU - Kuratieva, N. V.

AU - Sukhikh, A. S.

AU - Gromilov, S. A.

N1 - The work was supported by the Ministry of Science and Higher Education of the Russian Federation: synthesis and characterization of potassium and rubidium hexafluoroacetylacetonates were performed within project No. 121031700314-5, the crystal chemical study of potassium complexes was made within project No. 121031700313-8, the crystal chemical study of rubidium complexes was made within the program “Priority 2030”.

PY - 2023/1

Y1 - 2023/1

N2 - Complexes MI(hfac), where MI = K+, Rb+, (Formula Presented.) (hexafluoroacetylacetonate ion) are synthesized and characterized (elemental analysis, IR spectroscopy, powder X-ray diffraction analysis). It is shown that in the synthesis of K(hfac) from an ethylacetate (EtOAc) solution of K2CO3 and Hhfac taken in a stoichiometric ratio, at the intermediate stage, EtOAc molecules come into the K+ coordination sphere, and {K2(hfac)2(EtOAc)}∞ crystals are formed. At room temperature EtOAc is removed, and the K(hfac) target product is obtained. The twofold excess of Hhfac results in a mixture of products in which adduct crystals with water and hydrated β-diketone {K2(H4hfpt)2(hfac)2(H2O)}∞ (H4hfpt = 1,1,1,5,5,5-hexafluoropentane-2,2,4,4,-tetraol) are present. Slow crystallization of Rb(hfac) in and L-shaped ampoule at 35-40 °C in chloroform leads to the formation of {Rb3(hfac)2(CF3COO)(ttpt)}∞ (ttpt = 2,4,6-tris(trifluoromethyl)tetrahydropyrane-2,4,6-triol) crystals, and at crystallization in a drop of the 1.1 M NaCl solution, {Na2Rb(hfac)3}∞ crystals are found. By thermogravimetry it is shown that rubidium hexafluoroacetylacetonate is thermally less stable than similar complexes of potassium and cesium.

AB - Complexes MI(hfac), where MI = K+, Rb+, (Formula Presented.) (hexafluoroacetylacetonate ion) are synthesized and characterized (elemental analysis, IR spectroscopy, powder X-ray diffraction analysis). It is shown that in the synthesis of K(hfac) from an ethylacetate (EtOAc) solution of K2CO3 and Hhfac taken in a stoichiometric ratio, at the intermediate stage, EtOAc molecules come into the K+ coordination sphere, and {K2(hfac)2(EtOAc)}∞ crystals are formed. At room temperature EtOAc is removed, and the K(hfac) target product is obtained. The twofold excess of Hhfac results in a mixture of products in which adduct crystals with water and hydrated β-diketone {K2(H4hfpt)2(hfac)2(H2O)}∞ (H4hfpt = 1,1,1,5,5,5-hexafluoropentane-2,2,4,4,-tetraol) are present. Slow crystallization of Rb(hfac) in and L-shaped ampoule at 35-40 °C in chloroform leads to the formation of {Rb3(hfac)2(CF3COO)(ttpt)}∞ (ttpt = 2,4,6-tris(trifluoromethyl)tetrahydropyrane-2,4,6-triol) crystals, and at crystallization in a drop of the 1.1 M NaCl solution, {Na2Rb(hfac)3}∞ crystals are found. By thermogravimetry it is shown that rubidium hexafluoroacetylacetonate is thermally less stable than similar complexes of potassium and cesium.

KW - alkali metals

KW - hexafluoroacetylacetonates

KW - single crystal X-ray diffraction analysis

KW - thermal properties

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85149585695&origin=inward&txGid=07a9d131d13c645c80badd7660fc24e6

UR - https://www.mendeley.com/catalogue/1a56f7a0-d4a6-3186-84e5-506e7746d384/

U2 - 10.1134/S0022476623010055

DO - 10.1134/S0022476623010055

M3 - Article

VL - 64

SP - 82

EP - 96

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 1

ER -