Hydride Compounds of the Titanium and

HYDRIDE COMPOUNDS OF THE TITANIUM AND VANADIUM GROUP ELEMENTS... 

Hydride Compounds of the Titanium and Vanadium Group Elements... 

The reaction of metal alkyl compounds with dihydrogen, leading to hydride species with elimination of alkanes, is commonly observed for Lewis acidic metal centers. This reaction has been used to prepare hydride complexes of the lanthanides, and of titanium(III), see equation 8 [39]. 

Titanium iron hydrides are among the materials which, at the present time, appear to have potential for practical applications as an energy-storage medium (7). The formation and properties of titanium iron hydride have been studied by Reilly and Wiswall (3), who found that the reaction proceeds in two steps as indicated by Reactions 5 and 6. Both hydrides have dissociation pressures above 1 atm at room temperature in contrast to TiH2 which is very stable. Titanium iron is representative of intermetallic compounds that consist of an element (titanium) capable of forming a stable hydride and another element (iron) that is not a hydride former or at best, forms a hydride with great difficulty. Iron presumably plays a role in destabilizing the hydrides. Titanium also forms a 1 1 compound with copper (there are other intermetallic compounds in the titanium-copper system) and this fact, coupled with the observation that copper... 

Concomitant with continued olefin insertion into the metal-carbon bond of the titanium-aluminum complex, alkyl exchange and hydrogen-transfer reactions are observed. Whereas the normal reduction mechanism for transition-metal-organic complexes is initiated by release of olefins with formation of hydride followed by hydride transfer (184, 185) to an alkyl group, in the case of some titanium and zirconium compounds a reverse reaction takes place. By the release of ethane, a dimetalloalkane is formed. In a second step, ethylene from the dimetalloalkane is evolved, and two reduced metal atoms remain (119). 

Reductive 1,2-eIimination of chlorine and bromine from adducts of l-bromo-2-chlorocyclo-propene (see Section 5.2.2.1.2.5.) with oxygen and sulfur hetarenes has served in the synthesis of a number of cycloproparenes. This transformation is effected by low-valent titanium together with lithium aluminum hydride or an organolithium compound. Thus, reaction of the adduct 3 of l-bromo-2-chlorocyclopropene and 1,3-diphenylisobenzofuran with tita-nium(III) chloride and lithium aluminum hydride overnight in tetrahydrofuran led to elimination of both halogens together with extrusion of the oxygen and formation of 2,7-diphenyl-l/f-cyclopropa[ ]naphthalene (4) in 72% yield. 

While the connection between the structure of the hydrides and their pyrophoric behavior seems to be obscure, it should be pointed out that the compounds of hydrogen fall into three distinctive groups the above-described phosphines, silanes, and boranes, which have covalent bonds the salt-like hydrides of the alkali and alkaline earth metals and the interstitial, nonstoicbiometric or berthollide —type hydrides of the transition metals—e.g. the rare earths, titanium, and zirconium. Pyrophoric compounds are found in all three groups. 

In a related process the work is dipped in a catalytic titanium compound and then transferred to a bath of aluminium hydride solution. The solution dries leaving the hydride on the surface and mild heating then turns the hydride into metallic aluminium. The conversion stage occurs slowly at room temperature or in seconds at 100°C. 

Hydroalumination of terminal alkenes using EtjAl as the hydride source must be carried out with titanium catalysts [24], since zirconium compounds lead to the formation of alumacyclopentanes [60, 61] (Scheme 2-11) and carbometallated products [62]. Suitable substrates for hydroalumination include styrene, allylnaphthalene and vinylsilanes. Only one of the ethyl groups in EtjAl takes part in these reactions, allowing the synthesis of diethylalkylalanes, which are difficult to obtain by other methods. 

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