The Chemistry of Aluminum-Nitrogen Compounds: I. Reactions of Trimethylaluminum and Trimethylaluminum Trimethylamine With Several Methylhydrazines

Abstract

The reactions of trimethylaluminum and trimethylaluminum trimethylamine with various methylhydrazines have produced a number of complexes and polymers: with methylhydrazine, both Me3Al and Me3Al:NMe3 produce the polymer [—MeAlNHNMe—]n with 1,2-dimethylhydrazine, both produce the polymer [—Al(MeNNMe)1.5—]n; with 1,1-dimethylhydrazine, Me3Al produces [Me2Al—NHNMe2]2 and Me3Al:NMe3 produces the unusual complex Me2Al(NHNMe2) (NH2NMe2); with trimethylhydrazine, Me3Al produces [Me2Al—NMeNMe2]2 and Me3Al:NMe3 produces an isomer with the same formula but an as-yet-uncharacterized structure. In addition, the intermediate Me3Al:NHMeNMe2 has been isolated from the reaction of either Me3Al or Me3Al:NMe3 with trimethylhydrazine. With tetramethylhydrazine, Me3Al produces Me3Al:NMe2NMe2. The formation of the complexes with covalent aluminum–nitrogen bonds is specific and methane is the only gas eliminated during these reactions.

Reactions of Diethylberyllium and Diethylberyllium Trimethylamine With the Methylhydrazines

“…The reactions of Et2Be and EtzBe:Nfile3 with methylhydrazines follow the same general course observed for MesAl-hydrazine reactions (8). The following two general reactions, illustrated by the equations, show (1) the formation of a dative Be:N bond, and (2) the formation of a covalent Be-X bond by elimination of ethane:…”

Some Reactions of Organoaluminum Compounds With Nitrogen-Containing Bases

“…The apparatus and procedures employed have been described previously (1,4). The arni~les and hydrazines were distilled fro111 CaH?…”

Arsinohydrazines: reactions of hydrazine and substituted hydrazines with organo-arsine derivatives

“…In a somewhat similar situation, however, alkylalanes react at the least substituted nitrogen atom of dimethylhydrazine, suggesting that steric factors prohibit attack at the alternative, substituted site (12). It seems likely that similar factors would operate with (CF,),AsCl, giving rise to MeNHNHAs(CF,),, rather than its isomer.…”