Study of Potassium, Rubidium Hexafluoroacetylacetonates and by-Products of Their Synthesis and Crystallization

Synthesis, Structure, and Characterizations of a Volatile/Soluble Heterometallic Hexanuclear Precursor [NaMn2(thd)4(OAc)]2

“…The coordination of the sodium ion by two oxygen atoms from diketonate groups and three oxygen atoms from acetate ligands can be described as either distorted square pyramidal or distorted vacant octahedral, according to calculations by the Continuous Shape Measures (CShM) method [36,37]. An average Na-O bond distance of 2.367 (3) Å in 1 (Table 2) is typical for the 5-coordinated sodium ion in a diketonate/acetate coordination environment [22][23][24][25]. Each of the two µ 3 -acetates are chelating Na and bridging it with Mn on one end and with another Na on the other end.…”

“…While a Li ion commonly appears as tetrahedrally coordinated in heterometallic complexes with transition metals [1][2][3][19][20][21], Na prefers higher coordination numbers. It typically experiences a coordination number of five or six upon participation in chelating bridging frameworks [22][23][24][25][26][27][28][29][30]. Great illustrations of this statement are analogous tetranuclear complexes with an A:M = 1:1 ratio, [A 2 M 2 L 6 ] (A = Li, Na; M = transition metal) [27,31], where Na not only requires an additional coordination by THF molecules but also changes the whole ligand distribution within the heterometallic assembly.…”

Potassium and Cesium Fluorinated β-Diketonates: Effect of a Cation and Terminal Substituent on Structural and Thermal Properties

“…All individual β-diketonates M I (Me..C 2 F 5 )(H 2 O) X and M I (Me..C 3 F 7 )(H 2 O) (M I = K, Cs) 1-6 were obtained for the first time. Due to the high acidity of fluorinated β-diketones [29], it was possible to use a simple synthetic method through the neutralization of a metal carbonate at room temperature [25][26][27]. However, water is additionally formed as a product, which can potentially be included in the structure of the complexes.…”

“…The latter is expected to be dependent both on the β-diketonate ligand and HAM cation, but the available data are not yet sufficient to identify general trends. On the one hand, the works [25,27] demonstrated the absence of water in the structure of metal hexafluoroacetylacetonates (M(CF 3 ..CF 3 ), M = K, Rb, Cs) since M-F contacts effectively saturated the coordination environment of the cation. On the other hand, both the non-fluorinated potassium acetylacetonate [28] and the fluorinated HAM β-diketonates with an aromatic substituent [26,30] contained water molecules in the structures.…”

“…However, this requires the revealing of the fundamental relationships between the structure of complexes and their functional characteristics, i.e., the supplementation and systematization of relevant data. Previous studies were focused mostly on the effects of a non-fluorinated substituent with a fixed CF 3 group [25][26][27] or non-fluorinated complexes [28]. In this work, we continue the systematic study of alkali metal β-diketonates and analyze the effect of an increase in the length of the fluorinated substituent (from C 2 F 5 to C 3 F 7 ).…”