Rare-earth metal complexes derived from the acids Ph2C(X)CO2H (X= OH, NH2): Structural and ring opening polymerization (ROP) studies.
Collins, Jack; Santoro, Orlando; Prior, Timothy J.; Chen, Kai; Redshaw, Carl
Dr Timothy Prior T.Prior@hull.ac.uk
Senior Lecturer in Inorganic Chemistry
Professor Carl Redshaw C.Redshaw@hull.ac.uk
Professor of Inorganic Materials Chemistry and REF Lead for Chemistry
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 epsilon-caprolactone (epsilon-CL) and rac-lactide (r-LA) has been investigated herein. In the case of epsilon-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 epsilon-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.
Collins, J., Santoro, O., Prior, T. J., Chen, K., & Redshaw, C. (2021). Rare-earth metal complexes derived from the acids Ph2C(X)CO2H (X= OH, NH2): Structural and ring opening polymerization (ROP) studies. Journal of molecular structure, 1224, https://doi.org/10.1016/j.molstruc.2020.129083
|Journal Article Type||Article|
|Acceptance Date||Aug 12, 2020|
|Online Publication Date||Aug 13, 2020|
|Publication Date||Jan 15, 2021|
|Deposit Date||Aug 13, 2020|
|Publicly Available Date||Aug 14, 2021|
|Journal||Journal of Molecular Structure|
|Peer Reviewed||Peer Reviewed|
|Keywords||Lanthanide; Magic Acids; Diphenylglycine; Ring Opening Polymerization; Biodegradable|
This file is under embargo until Aug 14, 2021 due to copyright reasons.
Contact C.Redshaw@hull.ac.uk to request a copy for personal use.