Tantalum coordination numbers

It was assumed that tantalum, when added to the melt in the form of potassium heptafluorotantalate, K2TaF7, interacts with KF or KC1 to form a compound with an increased tantalum coordination number of up to eight. The compound is present in the melt in its dissociated form, yielding potassium ions and octa-coordinated complexes of tantalum, namely TaFg3 or TaF7Cl3. ... 

An increase in the Me F ratio leads to an increase in the acidity of the initial solution, whereas the acidity of alkali metals increases according to their molecular weight, from Li to Cs. Therefore the additives of fluorides of alkali metals having higher atomic weight provide formation of complex fluorides with lower coordination number of tantalum or niobium. 

The ratio between the anionic and cationic radii leads to coordination numbers, the lowest of which is 6, which correspond to a octahedral polyhedron of anions around a central cation [135]. In this case, the compound structure type depends on the ratio of total number of anions and cations. The total number of anions (X) is calculated by summing up the number of oxygen (O) ions and of fluorine (F) ions X=0+F, while the total number of cations (Me) is the number of tantalum ions, niobium ions and other similar cations. 

Since the coordination number of tantalum or niobium in fluoride and oxyfluoride compounds cannot be lower than 6 due to steric limitations, further decrease of the X Me ratio (lower than 6) leads to linkage between complex ions in order to achieve coordination saturation by sharing of ligands between different central atoms of the complexes. The resulting compounds have X Me ratios between 6 and 4, and form crystals with a chain-type structure. 

The structure of LiTa02F2, as reported by Vlasse et al. [218], is similar to a ReC>3 type structure and consists of triple layers of octahedrons linked together through their vertexes. The layers are perpendicular to the c axis, and each layer is shifted, relative to the layer below, by half a cell in the direction (110). Lithium atoms are situated in the centers of the tetragonal pyramids (coordination number = 5). The other lithium atoms are statistically distributed along with tantalum atoms (coordination number = 6) at a ratio of 1 3. The sequence of the metal atoms in alternating layers is (Ta-Li) - Ta - (Ta-Li). Positions of oxygen and fluorine atoms were not determined. The main interatomic distances are (in A) Ta-(0, F) - 1.845-2.114 Li-(0, F) - 2.087-2.048 (O, F)-(0,F) - 2.717-2.844. 

The lowest coordination number of tantalum or niobium permitted by crystal chemistry formalism is 6, which corresponds to an octahedral configuration. X Me ratios that equal 3, 2 or 1 can, therefore, be obtained by corresponding substitutions in the cationic sub-lattice. A condition for such substitution is no doubt steric similarity between the second cation and the tantalum or niobium ion so as to enable its replacement in the octahedral polyhedron. In such cases, the structure of the compound consists of oxyfluoride octahedrons that are linked by their vertexes, sides or faces, according to the compound type, MeX3, MeX2 or MeX respectively. Table 37 lists compounds that have a coordination-type structure [259-261]. 

X Me Second cation present, with coordination number greater than 6 (second cation s ionic radius > tantalum/niobium ionic radius) Only cations that can fit into/occupy octahedral voids are present (second cation s ionic radius tantalum/niobium ionic radius)... 

Three conceptual steps can be discerned in the definition of the ionic structure of fluoride melts containing tantalum or niobium. Based on the very first thermodynamic calculations and melting diagram analysis, it was initially believed that the coordination numbers of tantalum and niobium, in a molten system containing alkali metal fluorides, increase up to 8. 

S Tantalum and niobium are present in the crystal structure in the form of complex ions. The lowest coordination number, 6, corresponds to the formation of slightly distorted octahedrons. The linking and packaging of the octahedrons depends on the X Me ratio, where X is the total number of oxygen and fluorine atoms, and Me is the total number of tantalum or niobium ions as well as other metals that can replace tantalum or niobium in the octahedral polyhedron. The crystal structure type can be defined based on the X Me ratio, as follows ... 

Both the weight gain data from the reactions and the analyses of the products clearly showed that only the 1 to 1 adducts, TaCl5 py and TaBr5 py, were formed. These reactions gave no evidence of formation of a 2 to 1 adduct such as that reported by Lindner and Feit (11) for tantalum (V) chloride and pyridine— i.e., TaClg 2py. Thus it does not appear that tantalum may expand its coordination number beyond 6 in these compounds. The solids are hydrolyzed only slowly in water, which wets the surface of the solids with difficulty. 

The number of authenticated niobium and tantalum coordination compounds in oxidation state +1 is very limited. They were generally obtained through reduction of [MCl4(dmpe)2], [TaCl2(dmpe)2] or Nb(OC6H3Me2-3,5)2(dmpe)2.731a... 

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