Cluster compounds niobium halides

The known halides of vanadium, niobium and tantalum, are listed in Table 22.6. These are illustrative of the trends within this group which have already been alluded to. Vanadium(V) is only represented at present by the fluoride, and even vanadium(IV) does not form the iodide, though all the halides of vanadium(III) and vanadium(II) are known. Niobium and tantalum, on the other hand, form all the halides in the high oxidation state, and are in fact unique (apart only from protactinium) in forming pentaiodides. However in the -t-4 state, tantalum fails to form a fluoride and neither metal produces a trifluoride. In still lower oxidation states, niobium and tantalum give a number of (frequently nonstoichiometric) cluster compounds which can be considered to involve fragments of the metal lattice. 

Niobium and tantalum, though metallic in many respects, have chemistries in the V oxidation state that are very similar to those of typical non-metals. They have virtually no cationic chemistry but form numerous anionic species. Their halides and oxide halides, which are their most important simple compounds, are mostly volatile and are readily hydrolyzed. In their lower oxidation states they form an extraordinarily large number of metal-atom cluster compounds. Only niobium forms lower states in aqueous solution. The oxidation states and stereochemistries (excluding those in the cluster compounds) are summarized in Table 26-B-l. 

B. Peric, R. Gautier, C.J. Pickard, M. Bosiocic, M.S. Grbic, M. Pozek, Solid-state NMR/NQR and first-principles study of two niobium halide cluster compounds. Solid State Nucl. Magn. Reson. 59—60 (2014) 20—30. 

Just as, in Group VB, niobium, so, in this Group, molybdenum provides most of the examples of the chalcogenide halides. The occurrence and preparation of such compounds are described in numerous publications. In most cases, they have been obtained as powders, with the composition based on chemical analyses only. The presence of defined, homogeneous phases is, therefore, in many cases doubtful. In addition, some published results are contradictory. A decision is possible where a complete structure analysis has been made. As will be shown later, the formation of metal-metal bonds (so-called clusters), as in the case of niobium, is the most characteristic building-principle. Such clusters... 

The second class of hexanuclear clusters also contains an octahedron of metal atoms, but they are coordinated by twelve halide ligands along the edges (Fig. 16.64b). Niobium and tantalum form clusters of this type. Here the bonding situation is somewhat more complicated The metal atoms are surrounded by a very distorted square prism of (bur metal and four halogen atoms. Furthermore, these compounds are electron deficient in the same sense as the boranes—there are fewer pairs of electrons than orbitals to receive them and so fractional bond orders of are obtained. 

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