Bis(salicylamidine) Ligands (FAlen): A Variant of Salen with "à la Carte" Denticity.

Ethylene- and phenylene-bridged bis(salicylamidine) ligands have been readily prepared from ethylene or phenylenediamine and iminium chloride derivatives generated from ,-dialkylsalicylamides. The former, in its diprotonated form (FAlenH), reacts with AlMe to afford a zwitterionic dimethyldiphenoxyaluminate complex with the FAlen ligand monoprotonated and in a bidentate κ, fashion. A phenylene-bridged proligand behaves differently, yielding a neutral methylaluminum complex bearing a κ,,-coordinated FAlen ligand. From these complexes, methyl anion abstraction with B(CF) or a reaction with Schrock's alcohol leads to the corresponding aluminum cationic or alkoxy complexes in which a κ,,,-coordination mode of the FAlen ligand is observed. X-ray diffraction studies of the proligands and of the complexes show that the amidine functions feature a configuration when the -amidine atom is not coordinated to the metal and conversely a cis configuration when it is. Density functional theory calculations show that - isomerization of the amidine functions occurs upon coordination with the metal ion with very low energy barriers. They also confirm the intuition that the denticity of the FAlen ligands in the complexes is directly related to the electron richness of the metal ion. At last, FAlen Al complexes are used as initiators for the controlled ring-opening polymerization of -lactide to afford poly(lactic acid) with slight isotactic bias.