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 in situ from N,N-dialkylsalicylamides. The former, in its diprotonated form (FAlenH2), reacts with AlMe3 to afford a zwitterionic dimet...
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Veröffentlicht in: | Inorganic chemistry 2023-05, Vol.62 (19), p.7342-7352 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | Ethylene- and phenylene-bridged bis(salicylamidine) ligands have been readily prepared from ethylene or phenylenediamine and iminium chloride derivatives generated in situ from N,N-dialkylsalicylamides. The former, in its diprotonated form (FAlenH2), reacts with AlMe3 to afford a zwitterionic dimethyldiphenoxyaluminate complex with the FAlen ligand monoprotonated and in a bidentate κ2 O,O′ fashion. A phenylene-bridged proligand behaves differently, yielding a neutral methylaluminum complex bearing a κ3 O,N,O′-coordinated FAlen ligand. From these complexes, methyl anion abstraction with B(C6F5)3 or a reaction with Schrock’s alcohol leads to the corresponding aluminum cationic or alkoxy complexes in which a κ4 O,N,N′,O′-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 trans configuration when the N-amidine atom is not coordinated to the metal and conversely a cis configuration when it is. Density functional theory calculations show that trans–cis 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 rac-lactide to afford poly(lactic acid) with slight isotactic bias. |
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ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/acs.inorgchem.3c00493 |