Top Organomet Chem (2013) 41: 1–58 DOI: 10.1007/3418_2012_55 # Springer-Verlag Berlin Heidelberg 2012 Published online: 10 November 2012 Simple Trivalent Organoaluminum Species: Perspectives on Structure, Bonding, and Reactivity Janusz Lewin ´ski and Andrew E.H. Wheatley Abstract This chapter deals with the most significant developments in Al(III) organoaluminum chemistry since 2000. The most prominent synthetic and structural features along with reactivity trends are discussed for organoaluminum compounds featuring simple s-bonded substituents and the corresponding 4- and 5-coordinate complexes formed in the presence of Lewis base. The structural effects of including ligands with group 15 and 16 donors are discussed in terms of the formation of heteroatom bridges and the ubiquitous formation of cyclic motifs. The structural implications of using bidentate, chelating ligands are also introduced, including the propensity of these for stabilizing cationic Al(III) species. The current and potential utility of such species in areas such as catalysis and material science is also highlighted with, whenever appropriate, structure/reactivity correlations. Keywords Catalysis, Coordination chemistry, Material science, Organoaluminum, Reactivity, Structure Contents 1 Introduction ................................................................................. 3 2 Aluminum Trialkyls: Structures and Complexes with Lewis Bases ...................... 4 3 Organoaluminum Alkoxides and Aryloxides .............................................. 7 3.1 Derivatives of Alcohols and Phenols ................................................. 8 3.2 Derivatives of Alcohols with Donor Termini ........................................ 11 3.3 Derivatives of Diols ................................................................... 14 3.4 Complexes Supported by Bidentate Ligands with a Delocalized Bond System .... 15 3.5 Schiff Base Complexes and Related Structures ..................................... 17 J. Lewin ´ski (*) Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland Department of Chemistry, Warsaw University of Technology, Warsaw, Poland e-mail: lewin@ch.pw.edu.pl A.E.H. Wheatley Department of Chemistry, University of Cambridge, Cambridge, UK