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Synthesis and Structural Characterization of Various N,O,N-Chelated Aluminum and Gallium Complexes for the Efficient ROP of Cyclic Esters and Carbonates: How Do Aluminum and Gallium Derivatives Compare ?

The novel Al and Ga coordination compounds 4, 5, 7, and 8 of the type (NON)AlX (NON2– = {RNC6H4}2O2–; 4, R = Cy, X = Me; 5, R = C5H9, X = OCH2Ph; 7, R = C6F5, X = Me) and (NON)GaX (NON2– = {R2NHC6H4}2O2–; 8, R = C6F5, X = Me) have been synthesized via, in the case of 4, 7, and 8, a methane elimination reaction between the corresponding protio ligands (NON)H2 and MMe3 precursors (M = Al, Ga). The Al alkoxide derivative 5 was prepared via an alcoholysis reaction between κ3-N,O,N-{(C5H9)NC6H4}2O}2AlNMe2 and PhCH2OH. The tetracoordinate Al–THF adduct κ2-N,N′-{(C5H9)NC6H4}2O}2Al(Me)(THF) (6) was prepared via a methane elimination reaction between the protio ligand TfNONH2 (Tf = CF3SO2, 1c) and AlMe3 in a CH2Cl2/THF solvent mixture. As determined from X-ray studies, complexes 4, 7, and 8 are monomeric in the solid state and feature a central tetracoordinate metal center effectively κ3-N,O,N′ chelated and adopting a trigonal-monopyramidal geometry. The presence of Ga···F(o-C6F5) contacts in the solid-state struc...

Authors:   Frédéric Hild; Nirvana Neehaul; Frédéric Bier; Morgane Wirsum; Christophe Gourlaouen; Samuel Dagorne
Journal:   Organometallics
Year:   2013
DOI:   10.1021/om3011068
Publication date:   11-Jan-2013
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