204518-41-2Relevant academic research and scientific papers
Monomeric Alanes: Synthesis, Structure, and Thermolysis of Mes* Al(H)N(SiMe3)2 and a One-Pot Synthetic Route to Mes*2AIH (Mes* = -C6H2-2,4,6-t-Bu3)
Wehmschulte, Rudolf J.,Power, Philip P.
, p. 2106 - 2109 (2008/10/08)
The reaction of (Mes*AlH2)2 (Mes* = -C6H2-2,4,6-t-Bu3) with HN(SiMe3)2 affords the monomeric amidoarylalane Mes* Al(H)N(SiMe3)2, 1. This product can also be synthesized by the reaction of [Mes*AlH2]2 with LiN(SiMe3)2, which, in addition, yields the byproducts LiAlH2{N(SiMe3)2}2, 3, and Mes*H. Thermolysis of 1 at 175-180 °C affords three different products: Mes*AlC6H2-2,4-t-Bu2-6-CMe 2CH2, 2, the related species (Me3Si)2NAlC6H2-2,4-t-Bu2-6-CMe2CH2, 4, and the imide [Mes*AlN(SiMe3)]n, 5. In addition, the previously reported monomeric alane Mes*2AlH was synthesized in ca. 70% yield by a one-pot reaction between LiMes* (generated in situ) and AlH3·NMe3. All products were spectroscopically characterized, and the structure of 1 was determined by X-ray crystallography. The Al-N distance (1.819(2) A) in 1 is relatively long. However, it has a substantial, 18.5 kcal mol-1, Al-N rotation barrier which is attributed to steric congestion rather than Al-N π bonding.
