Aluminum organometallic compounds were among some of the first organometallics to be developed. However, their history until present times has been dominated by single new developments. For example, the ‘aufbaureaktion’ revealed the unique oligomerization chemistry of aluminum alkyls in the 1950s. This was followed in the 1980s by the discovery that hydrolyzed aluminum compounds, for example, methylaluminoxanes, could be used as co-catalysts in olefin polymerization. Since that time, there has been an explosion in the utility of alkylaluminum compounds in every area of chemistry, including biological studies, a remarkably diverse usage in Lewis acid catalysis, materials science, organic syntheses, and theoretical studies. This has led to a wide range of reviews published on this subject since 1993. This chapter will provide guidance to this enormous body of literature, but will focus on important highlights that will provide a general introduction to the diverse chemistry of aluminum compounds. These highlights include a new understanding of the reactivity of alkylaluminum compounds with oxygen, water, alcohols, and new insertion reactions. The cationic chemistry of aluminum has been firmly established over the past decade and is now well understood. Both low-coordinate compounds and those supported by chelate ligands will be covered here. Furthermore, important new advances have been made in hydroaluminations and the formation of new compounds that are difficult to classify, but that will provide a view of where the field of aluminum alkyl chemistry is heading in the next decade.
Keywords
Aluminum; Aluminum alkyl; Aluminum fluoride; Catalysis; Five coordinate; Hydroalumination; Lewis acid; Multiple bonding; Organoaluminum