Aluminium amides

The simplest aluminium amides have hydrogen substituents and the generation of species such as H2AINH2, HAINH2 and AIN H2 has been reported via the insertion of the metal atom 

Stable aluminium amides with terminal —NH2 groups are rare. A simple example is [Al-(NH2)2( N(Dipp)C(Me) 2CH)], which was obtained by ammonolysis of the corresponding dichloride the Al—NH2 bond lengths are 1.789(4) A. The reaction of the Li N(H)Pr with 

AICI3 in the presence of H2NPr afforded the unusual species [AlCl3(NH2Pr )2 Al(NH2)-NH3 AlCl(NHPr )NP ]2] 5 The Al Ml, distance is 1.880(6) A. 

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Finally, mention can be made of the more exceptional titrants for inert media, such as sodium triphenylmethane, lithium aluminium hydride and lithium aluminium amide. 

Lithium aluminium amide this amide was introduced by Higuchi et al.102 because it yields true acid-base reactions ... 

Four-coordinate, monomeric aluminium amides. Monomeric, four-coordinate aluminium amido derivatives are now quite numerous, yet none had been structurally characterized before 1980. They may be divided into two broad categories those which are Lewis base adducts and those in which four-coordination for aluminium is a result of complexation by a chelating ligand. 

Aluminium complexes of chelating amido ligands are perhaps the most common type of monomeric four-coordinate aluminium amide. A full listing of such complexes will not be provided and selected examples will suffice to illustrate synthetic approaches and... 

Higher coordinate monomeric aluminium amides. The distorted square pyramidal... 

A very large number of mixed metal aluminium amides has been reported. The majority are lithium-aluminium amide salts that exhibit a variety of different structures. Only a small number of ese compounds are discussed here.39,52,57,72,118-138 simplest is LiAl-(NH2)4 produced from the reaction of lithium and aluminium in liquid ammonia at 80 to 100 °C. The atomic arrangement of LiAl(NH2)4 has been studied by IR-spectroscopy and single crystal X-ray crystallography and was found to be a new variant of the GaPS4-type structure. 

The most fascinating lower oxidation state aluminium amides are the series of... 

MeaQH3, or Pr 0) on diethanolamine affords the bicyclic compound (429) rather than (430). 2 The presence of aluminium in an eight-membered ring is postulated in (431), a proposed intermediate in the formation of a trimeric aluminium amide by heating iV-diethylaluminium-AW-diphenylamine. The tetrasulphide (432) is formed, with other compounds, in the reaction shown, and is oxidized to the sulphoxide (433) by peracid the tetra-phosphorus compound (434) has been prepared in 0.3 % yield. ... 

Isomerization of oxirans with organo-aluminium amides is a mild and very stereospecific new method/ governed by approach of the aluminium compound from the least hindered side of the oxiran and a boat-like transition state for proton abstraction typical examples are (27) - (28) and (29) - (30). 

A one-step conversion of esters into nitriles is now available/ a significant improvement over existing methodology for the same transformation. This apparently general synthetic procedure utilizes the easily generated dimethyl-aluminium amide, a reagent compatible with a wide variety of functional groups (Scheme 20). 

Lithium aluminium amide, LiAKNH ).-preparation, X-ray investigation, ir spectrum, and thermal decomposition, H. Jacobs, K. JSnichen, C. Hadenfeldt and R. Juza, Z.Anorq.Allq.Chem.. 1985, 531. 125. 

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