Complex hydrides alanate

R.A. Vatin, Ch. Chiu, T. Czujko, Z. Wronski, Feasibilty study of the direct mechano-chemical synthesis of nanostructured magnesium tetrahydroaluminate (alanate) [Mg(AIH )J complex hydride, Nanotechnology 16 (2005) 2261-2274. 

The mechanism of reduction by boranes and alanes differs somewhat from that of complex hydrides. The main difference is in the entirely different chemical nature of the two types. Whereas complex hydride anions are strong nucleophiles which attack the places of lowest electron density, boranes and alanes are electrophiles and combine with that part of the organic molecule which has a free electron pair [119]. By a hydride transfer alkoxyboranes or... 

Similar reductions are achieved by trialkylboranes [S26]. These reactions, although different in nature from the reductions by hydrides and complex hydrides, were amongst the first applications of boranes and alanes for the reduction of organic compounds. 

Reagents of choice for reduction of epoxides to alcohols are hydrides and complex hydrides. A general rule of regioselectivity is that the nucleophilic complex hydrides such as lithium aluminum hydride approach the oxide from the less hindered side [511, 653], thus giving more substituted alcohols. In contrast, hydrides of electrophilic nature such as alanes (prepared in situ from lithium aluminum hydride and aluminum halides) [653, 654, 655] or boranes, especially in the presence of boron trifluoride, open the ring in the opposite direction and give predominantly less substituted alcohols [656, 657,658]. As far as stereoselectivity is concerned, lithium aluminum hydride yields trans products [511] whereas electrophilic hydrides predominantly cis products... 

Reduction of unsaturated ketones to unsaturated alcohols is best carried out Nit v complex hydrides. a,/3-Unsaturated ketones may suifer reduction even at the conjugated double bond [764, 879]. Usually only the carbonyl group is reduced, especially if the inverse technique is applied. Such reductions are accomplished in high yields with lithium aluminum hydride [879, 880, 881, 882], with lithium trimethoxyaluminum hydride [764], with alane [879], with diisobutylalane [883], with lithium butylborohydride [884], with sodium boro-hydride [75/], with sodium cyanoborohydride [780, 885] with 9-borabicyclo [3.3.1]nonane (9-BBN) [764] and with isopropyl alcohol and aluminum isopro-... 

Sodium alanate (NaAll-14) remains so far the most studied complex hydride. It is found that NaAlH4 decomposes in several steps ... 

FIGURE 9.2 Trend of hydrogen weight fraction for various alanate compounds and cations as a function of the molecular weight of the compound. The trend is also representative of other complex hydrides, such as borohydrides. 

Solid-state nuclear magnetic resonance (NMR) has been extensively used to assess structural properties, electronic parameters and diffusion behavior of the hydride phases of numerous metals and alloys using mostly transient NMR techniques or low-resolution spectroscopy [3]. The NMR relaxation times are extremely useful to assess various diffusion processes over very wide ranges of hydrogen mobility in crystalline and amorphous phases [3]. In addition, several borohydrides [4-6] and alanates [7-11] have also been characterized by these conventional solid-state NMR methods over the years where most attention was on rotation dynamics of the BHT, A1H4, and AlHe anions detection of order-disorder phase transitions or thermal decomposition. There has been little indication of fast long-range diffusion behavior in any complex hydride studied by NMR to date [4-11]. 

The calculations presented here are consistent with many models and measurements described in the literature [11-14, 17, 20, 21], Models and measurements indicate that the effective thermal conductivity of particles loaded in a packed bed is generally limited to values below 5 W/m K, even with significant increases in the particle thermal conductivity (Fig. 4.4(b)). More clever methods must be employed to enhance thermal conductivity to levels above 5 W/m K. Additionally, the models discussed above have been developed for distinct particles typical of classic/interstitial hydride materials. These classic/interstitial beds are generally characterized as unsintered powders while complex hydrides, such as sodium alanates, can become porous sintered solids as seen in Fig. 4.5. Application of packed particle models have not been directly applied to sintered solid materials. 

In this section, we will explore the safety properties of a specific set of complex hydrides, sodium alanates. These materials represent the most advanced solid-state hydrogen system developed to date and allow us to understand the safety properties associated with this class of materials. 

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