Treatment of Ln(NO3)3.6H2O (Ln = La, Ce) with an equimolar amount of 2,2′-diphenylglycine (DpgH) in ethanol afforded the corresponding hexacoordinated complexes (DpgH±)3Ln(NO3)3.H2O (DpgH± = zwitterionic 2,2′-diphenylglycine, Ln = La (1), Ce (2)). The spectroscopic and structural features of these compounds have been investigated. Similar reactions with the related benzilic acid (BenzH2) were unsuccessful. The catalytic behaviour of 1 and 2 in the homo- and copolymerization of ε-caprolactone (ε-CL) and rac-lactide (r-LA) has been investigated herein. In the case of ε-CL, the two complexes exhibited comparable activity, allowing for complete monomer conversion under aerobic and solvent-free conditions at 150 °C in 24 h. With respect to the ROP of r-LA, 1 was found to be completely inactive, while only 8% conversion was achieved in the presence of 2. Liquid oligomers were isolated during ε-CL/r-LA co-polymerization in the presence of both complexes. The catalytic activity of the pre-ligands DpgH and BenzH2 (i.e. metal-free) was also examined. Interestingly, only BenzH2 was found to be active, although it required a higher catalyst loading and the presence of benzyl alcohol as co-activator.
Rare-earth metal complexes derived from the acids Ph2C(X)CO2H (X= OH, NH2): Structural and ring opening polymerization (ROP) studies
Santoro O.;
2021-01-01
Abstract
Treatment of Ln(NO3)3.6H2O (Ln = La, Ce) with an equimolar amount of 2,2′-diphenylglycine (DpgH) in ethanol afforded the corresponding hexacoordinated complexes (DpgH±)3Ln(NO3)3.H2O (DpgH± = zwitterionic 2,2′-diphenylglycine, Ln = La (1), Ce (2)). The spectroscopic and structural features of these compounds have been investigated. Similar reactions with the related benzilic acid (BenzH2) were unsuccessful. The catalytic behaviour of 1 and 2 in the homo- and copolymerization of ε-caprolactone (ε-CL) and rac-lactide (r-LA) has been investigated herein. In the case of ε-CL, the two complexes exhibited comparable activity, allowing for complete monomer conversion under aerobic and solvent-free conditions at 150 °C in 24 h. With respect to the ROP of r-LA, 1 was found to be completely inactive, while only 8% conversion was achieved in the presence of 2. Liquid oligomers were isolated during ε-CL/r-LA co-polymerization in the presence of both complexes. The catalytic activity of the pre-ligands DpgH and BenzH2 (i.e. metal-free) was also examined. Interestingly, only BenzH2 was found to be active, although it required a higher catalyst loading and the presence of benzyl alcohol as co-activator.
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