Niobium simple complexes

Dioxygen binds to metal porphyrins in the three expected modes, i.e. u-superoxo, peroxo and bridging peroxo. In contrast to die simple complexes discussed previously, dioxygen coordination occurs with a wide range of transition metals from titanium and niobium through to the Group VIII metals. 

Hydroamination is an atom-economical process for the synthesis of industrially and pharmaceutically valuable amines. The hydroamination reaction has been studied intensively, including asymmetric reactions, and a variety of catalytic systems based on early and late transition metals as well as main-group metals have been developed." However, Group 5 metal-catalysed hydroaminations of alkenes had not been reported until Hultzsch s work in 2011. Hultzsch discovered that 3,3 -silylated binaphtho-late niobium complex 69 was an efficient catalyst for the enantioselective hydroaminoalkylation of iV-methyl amine derivatives 70 with simple alkenes 71, giving enantioselectivities up to 80% (Scheme 9.30). Enantiomerically pure (l )-binaphtholate niobium amido complex 69 was readily prepared at room temperature in 5 min via rapid amine elimination reactions between Nb(NMe2)5 and l,l-binaphthyl-2-ol possessing bullqr 3,3 -silyl substituents. Since the complex prepared in situ showed reactivity and selectivity identical... 

On the other hand, efficient catalytic dimerization of simple alkenes can be usually achieved by early transition metal alkene or diene complexes. For example the niobium-butadiene complexes 44 and 45 also showed good catalytic activity for dimerization of isoprene into a mixture of the head-to-tail and head-to-head dimers 46 and 47 (Scheme 20). The former catalyst gave products in 85 15 ratio and the latter one gave rise to 70 30 ratio [26]. 

Pegmatite-containing niobium ores can be relatively complex and may contain biotite, enargite, albite, feldspar and ziron as the main gangue minerals. Some pegmatite ores (Araxa, Brazil) have a simple gangue composition, consisting mainly of quartz. 

Titanium is the most abundant metal in the earth crust, and is present in excess of 0.62%. It can be found as dioxy titanium and the salts of titanium acids. Titanium is capable of forming complex anions representing simple titanites. It can also be found in association with niobium, silicates, zircon and other minerals. A total of 70 titanium minerals are known, as mixtures with other minerals and also impurities. Only a few of these minerals are of any economic importance. 

Niobium and titanium incorporation in a molecular sieve can be achieved either by hydrothermal synthesis (direct synthesis) or by post-synthesis modification (secondary synthesis). The grafting method has shown promise for developing active oxidation catalyst in a simple and convenient way. Recently, the grafting of metallocene complexes onto mesoporous silica has been reported as alternate route to the synthesis of an active epoxidation catalyst [21]. Further the control of active sites, the specific removal of organic material (template or surfactant) occluded within mesoporous molecular sieves during synthesis can also be important and useful to develop an active epoxidation catalyst. Thermal method is quite often used to eliminate organic species from porous materials. However, several techniques such as supercritical fluid extraction (SFE) and plasma [22], ozone treatment [23], ion exchange [24-26] are also reported. 

Niobium oxide (niobia) is an active catalyst, and can be used as a support for metal nanoparticles or oxides, and it can serve as a promoter in some reactions ([43 5] and references therein). Catalytic applications of niobia include the Fischer-Tropsch synthesis, oxidative dehydrogenation of alkanes, and oxidative coupling of methane. Studies on high-surface-area niobium oxides are complicated by a high degree of complexity because several stable structures (NbO, NbO and Nb O ) exist and the resulting surfaces of high-surface-area niobium oxides are not simple truncations of bulk niobia structures. This is even more so for supported metal oxides when two-dimensional thin films of niobium oxide partially cover a support oxide (Al Oj, SiOj, ZrOj, TiOj, [43]). Nb Oj was also used as a support for V, Cr, Re, Mo, and W oxide overlayers [45, 46]. 

The unsubstituted para-t-butyl calixarenes themselves complex metals via their aryloxide groups. Since aryloxide complexes are frequently oligomeric, the simple calixarenes do not give monomeric complexes. Aryloxides are hard ligands, therefore they readily form complexes with oxo-philic hard metal ions such as alkali metals, early transition metals, lanthanides, and actinides. Complexation is often inferred because the calixarene acts as a carrier for the metal ion from an aqueous to an organic phase. With the /wa-/-butylcalix[ ]arenes in alkaline solution, a value of n = 6 gives the best carrier for lithium(I), sodium(I), and potassium(I), with a value of n 8 giving the best carrier for rubidium(I) and caesium(I).15,16 Titanium(IV) complexes have been characterized,17-19 as well as those of niobium(V) and tantalum(V).20-22 These complexes are classified as... 

Further substitution of niobium results in exceedingly complex structures, and a micrograph of a typical crystal of the niobium end-member of the series, BiuNbzOn, is illustrated in Fig. 11. The unit cell of this material is extremely large, approximately 115 x 80 X 5 5 A, and the x-ray powder diffraction diagram is impossible to interpret. From the micrograph shown, it would appear that the structure is based upon different principles from the one described above, but it can nevertheless be derived from it by repeated overlap of layers on (112) and (113) planes in a very complex sequence. Why such a complex sequence should be employed, and whether either of these phases are true "phases", or merely certain compositions in a quasi-continuous solid solution series, is not yet certain. What is however, demonstrated, is the remarkable ability which these simple layered structures show to variations in stoichiometry. 

In the 8-phase of niobium hydride, NbHo.ei, the additional structure observed in both the A and E modes remained in the spectrum of NbHo.03 Do.57 and the coupling model was dismissed [54].An explanation in terms of minor structural differences between the neighbouring sites in this phase was favoured. The degree of detail that can be extracted from more complex materials than the simple metals is limited and the spectra of TbNiAI H, 4 and UNiAl H2.0 are cases in point [55]. 

In fact, apart from controlled laboratory atmospheres, the gas is always complex in the multi-oxidant sense since even nitrogen in air can form nitrides with some alloy systems in addition to the oxides formed by the oxygen. This is seen particularly in alloys containing metals such as chromium, titanium, and niobium, where the formation of nitrides in air atmospheres interferes with the simple oxidation situation that is observed when using pure oxygen, or oxygen-argon mixtures. ... 

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