Niobium trivalent

Simultaneous fluorination of niobium oxide and oxides of trivalent metals using an ammonium hydrofluoride melt leads only to oxide-type compounds, MinNbC>4 due to low thermal stability of fluoride or oxyfluoride compounds that contain both niobium and trivalent metals. 

The radius of the second cation in known MuNbOFs, MU2Nb03F3 and Mul2Nb05F compounds containing bi- and trivalent metals, is usually similar to that of niobium s ionic radius. Such compounds cannot be considered as having an island-type structure and will be discussed later on. Only bismuth-containing compounds (Bi3+) display the presence of different cationic sublattices in their crystal structure. 

Oxyfluoroniobates, M2Nb05F, containing trivalent metals (where M = Ti, V, Cr) have the same type of structure [264], except for Cr2Nb05F, which has a tri-rutile type structure. This exception is related to the ordered, rather than statistical, distribution of chromium and niobium cations in the oxyfluoride octahedrons, which leads to a corresponding increase in cell parameter c. 

Trivalent cations are present in most of niobium oxychloride cluster compounds known to date and play an important role in their structural chemistry. The series AxNb6Cli202 (A = K, Rb, Cs, In), on the other hand, represents an example of an oxychloride structure stabilized without a trivalent counter-ion (Fig. 6.12). 

Vanadium pentoxide can be reduced to the metal by the action of hydrogen at high temperatures and pressures niobium pentoxide is more stable, and yields the trivalent oxide Nb203, whereas tantalum pentoxide has not hitherto been reduced by hydrogen. 

In addition to the halides the only trivalent salt of niobium is the uncertain double sulphate (NH4)2S04.Nba(S04)3.6H80. Tantalum has not given any trivalent salts. 

It is convenient here to include fluorides with a metal-to-fluorine ratio of 1 2.5. There are three examples. The chromium (53) and manganese (54) compounds, which are not isostructural, can be considered of the type, MF2,MF3, containing di- and trivalent metals. The niobium compound (35) is the only example of a metal cluster fluoride reported as yet. 

From the above discussion it follows that tetravalent and hexavalent thorium, uranium, and plutonium can be separated from the trivalent rare-earth fission products by taking advantage of differences in complexing properties. More highly charged cation fission products, such as tetravalent cerium and the fifth-period transition elements zirconium, niobium, molybdenum, technetium, and ruthenium, complex more easily than the trivalent rare-earths and are more difficult to separate from uranium and plutonium by processes involving complex formation. 

Trivalent lanthanocene complexes that are isoelectronic (14e, (P) to cationic group 4 metallocenes are also active for olefin polymerization, although their activity is much less than that of Ti and Zr [28,29]. Mashima et al. have reported monocyclopentadienyl rf-diene complexes of tantalum and niobium that are isoelectronic to group 4 metallocenes. These complexes catalyze ethylene polymerization, albeit with low activity [30]. 

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