Abstract
hydride and halide. Selected systems containing other Group 13 elements are also included when they contribute to the understanding of organoaluminum systems. This review includes small to large molecular systems and mono to polyaluminum species that have been studied by a wide variety of methods from molecular orbital analysis and semiempirical methods to the most elaborate wave-function correlated methods. The electronic structures are presented, and the structure–electronic structure relationships are discussed. The calculations illustrate how the oxidation states and the coordination number influence the structural and electronic properties of the complexes. The Lewis acid character of AlIII, the polarity of the Al(δ+)–C(δ−) bond, and the rarity of the multiple bond to Al appear as the leading factors. Carbon monoxide, alkyl, alkene, alkyne, aryl, cyclopentadienyl, and arene complexes of aluminum are described in detail. The polyaluminum species include systems with direct Al–Al interaction or interaction by way of bridging groups. The structures and role of methyl aluminum oxides (MAO) on polymerization are presented. The chapter ends with the description of mechanisms for reactions of selected organoaluminum reagents derived from computational studies.