Synthesis, Characterization, and Symmetry Relations of the Crystal Structures of Some Bis(dioxane) Adducts of Group 1 / Group 13 Heterometallic Trifluoroacetates

Abstract

Four bis(dioxane) adducts of mixed‐metal trifluoroacetates, M[M′(O2CCF3)4(C4H8O2)2] (M = Na, K, Cs, M′ = In and M = Cs, M′ = Ga) were synthesized by reaction of alkali metal trifluoroacetate and group 13 element trifluoroacetate in 1,4‐dioxane and completely characterized including X‐ray structure determination. Geometric parameters, empirical bond valences and frequencies of the symmetric C=O stretching vibrations show that the moisture sensitive solids are composed of dimeric structural moieties with site symmetry 1, containing alkali metal ions and bis(dioxane)tetrakis(trifluoroacetato)indate or ‐gallate ions. The dimeric units are further connected by weaker “intermolecular” dioxane interactions to neighboring alkali metal ions. Closer inspection of space group symmetry, unit cell parameters and atom sites allows to rationalize the compounds as members of two isotypic pairs that are further closely related due to the group‐subgroup relation of their monoclinc space groups to a common orthorhombic supergroup.

Oxidation of europium with ammonium perfluorocarboxylates in liquid ammonia: pathways to europium(ii) carboxylates and hexanuclear europium(iii) fluoridocarboxylate complexes

“…1 More recently, metal trifluoroacetates gained attention as precursors for metal fluorides, the trifluoroacetato ligand being the fluoride source. 2 Functional fluoridic thin-films or nanomaterials may be accessed this way. 3 Furthermore, the trifluoroacetate ion proves to be an efficient ligand to stabilize low oxidation states of the d-block metals 4 as well as subvalent oxidation states of heavy main group metals as in the case of the dibismuth( ii ) tetrakis (trifluoroacetate) molecule.…”