Titanium, Zirconium, Hafnium, Niobium, and Tantalum

The sensitivities to air of the compounds SnfSC6Fs)4 Ti(SC6Fs)4 Hf(SC6Fs)4 Nb(SCeF6)4 TaCls(SC6F6)a, obtained when solutions of the respective metal halides are heated under reflux with pentafluorothiophenol, increase in the order shown.  

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Barraclough et studied the infrared specda of a number of metal (aluminium, titanium, zirconium, hafnium, niobium, and tantalum) alkoxides and tentatively assigned the v(C-0)M and v(M-O) bands in these derivatives. It has been observed... 

Garvie, R. C. 1970. Oxides of Rare Earths, Titanium, Zirconium, Hafnium, Niobium, and Tantalum. In High temperature oxides. Part II. Ed. M. A. Alper, Academic Press, San Diego, CA. 

We have found tantalum to be especially suitable for synthetic reactions and equilibrations involving elements and their reduced halides which lie to the left of group V in the periodic table, namely the alkali metals and alkaline earth metals scandium, yttrium, and the lanthanides titanium, zirconium, hafnium, thorium, and uranium. Tantalum and niobium are also uniquely suitable containers for the syntheses of their own lowest halides, for example, Ta6Br14 3 and CsNb6In.4 Tantalum containers have been extensively employed for the synthesis of halides, but reduced compounds of some other nonmetals, some oxides, for example, perhaps can be handled as well. 

Nitrogen and carbon are the most potent solutes to obtain high strength in refractory metals (55). Particulady effective ate carbides and carbonitrides of hafnium in tungsten, niobium, and tantalum alloys, and carbides of titanium and zirconium in molybdenum alloys. 

Hydrogen reduction has a major advantage in that the reaction generally takes place at lower temperature than the equivalent decomposition reaction. It is used extensively in the deposition of transition metals from their halides, particularly the metals of Groups Va, (vanadium, niobium, and tantalum) and Via (chromium, molybdenum, and tungsten). The halide reduction of Group IVa metals (titanium, zirconium, and hafnium) is more difficult because their halides are more stable. 

The group IV B elements titanium, zirconium, and hafnium exhibit the normal isotope effect. Most of the data for the titanium-hydrogen system have been obtained at elevated temperatures. However, extrapolation of the available data (II, 13,31) to room temperature indicates a normal effect for hydrogen and deuterium. The group VB metals vanadium, niobium, and tantalum, on the other hand, exhibit inverse isotope effects indeed, these are the only pure metals that exhibit the inverse effect near room temperature. Extensive data have been reported for these systems. The P-C-T data obtained by Wiswall and Reilly (32) for vanadium hydrogen and deuterium clearly show a greater stability for... 

To date no tetrazole complexes appear to have been reported for the following triads scandium, yttrium, and lanthanum titanium, zirconium, and hafnium and vanadium, niobium, and tantalum. 

Hala, J. Halides, Oxyhalides and Salts of Halogen Complexes of Titanium, Zirconium, Hafnium, Vanadium, Niobium and Tantalum, Vol, 40, Elsevier Science, New York, NY, 1989. 

In this paper we review the results of our systematic work on the catalytic and adsorptive properties of transition metal carbides (titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, and iron). We focus our attention on the oxidation of hydrogen, carbon monoxide, ammonia, and the oxidative coupling of methane. The first two reactions are examples of complete (non-selective) oxidation, while the oxidation of ammonia simulates a selective oxidation process. The reaction of oxidative coupling of methane is being intensively explored at present as a means to produce higher hydrocarbons.5 10... 

A. Titanium, Zirconium, Hafnium, Vanadium, Niobium, and Tantalum... 

Monomeric species M OR-tert)x have been characterized for titanium, vanadium, chromium, zirconium, and hafnium (x = 4) and for niobium and tantalum (x == 5). With chromium it was found that limiting Cr(III) to coordination number 4 in the dimeric Cr2(OBu )e caused instability and a remarkable facility toward valency disproportionation or oxidation to the stable quadricovalent Cr(OBu )4 (8, 9). In contrast, molybdenum formed a stable dimeric tri-tert-butoxide (Bu O)3Mo=Mo-(OBu )3 which is diamagnetic and presumably bound by a metal-metal triple bond (10, II). Yet another interesting feature of chromium is the synthesis of a stable diamagnetic nitrosyl Cr(NO) (OBu )3 in which the nitric oxide is believed to act as a three-electron donor with formation of a four-coordinated low spin chromium (II) compound (12). The insta-bihty of Cr2(OBu )e and the stability of both Cr(NO) (OBu )3 and Cr(OBu )4 must result from the steric effects of the tertiary butoxo groups since the less bulky normal alkoxo groups form very stable polymeric [Cr(OR)3]a. compounds in which the Cr(III) has its usual coordination number of 6 (octahedral). 

The transition metal carbides and nitrides have often been called interstitial compounds [70] however, this is somewhat misleading. The small boron, carbon, or nitrogen atoms certainly occupy octahedral or trigonal prismatic voids of the metal sublattice, but the arrangement of the metal atoms themselves is different from that of the element. In the monocarbides the transition metal atoms show cubic close packing. However, titanium, zirconium, and hafnium are packed hexagonally and vanadium, niobium, and tantalum are body centered cubic [1]. Thus, these monocarbides are inorganic compounds with their individual crystal structures and they should not be considered as an interstitial compound of a transition metal host lattice. 

Mesoporous oxides from elements other than sihca have been reported as early as 1994. Cieslaetal. [169] found that metals such as Sb, Fe, Zn, Pb,W, and Mo also form mesoporous oxides. However, many of the mesophases obtained were lamellar and were not porous after template removal (calcination). Antonelli and Ying reported the transformation of titanium, niobium, and tantalum alkoxides into stable mesophases [170]. Subsequently, mesoporous oxides based on zirconium, hafnium, and manganese have been synthesized (for a recent review on these materials see [171]). Bagshaw and Pinnavaia [172] prepared mesoporous alumina with worm-like pores and a specific surface area of more than 400 m g . Mesoporous alumina with surface areas above 700 m g have been reported by Vaudry et al. [173]. 

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