Synthesis and Structure of the (µ2-OP(O)Ph2)-Linked Dimeric Amide Lanthanum Complex {[ CP(O)Ph2]La[N(SiMe3)2](µ2-OP(O)Ph2)}2 Bearing the Tridentate Heteroscorpionate Ligand. Investigation of the Catalytic Activity in rac-Lactide and ε-Caprolactone Polymerization

Author:

Rad’kova N. Yu.1,Cherkasov A. V.1,Trifonov A. A.12

Affiliation:

1. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhny Novgorod, Russia

2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia

Abstract

The dimeric amide lanthanum complex {[CP(O)Ph2]La[N(SiMe3)2](µ2-OP(O)Ph2)}2 (PzlMe2 is 3,5-dimethylpyrazole) bearing the N,N,O-tridentate heteroscorpionate ligand is synthesized. As found by X-ray diffraction (XRD) (CIF file CCDC no. 2212274), the complex is binuclear and its lanthanum ions are linked by two bridging monoanionic diphenyl phosphinate ligands. The synthesized lanthanum complex demonstrates a high catalytic activity in the polymerization with ring opening of rac-lactide and ε-caprolactone providing the quantitative conversion of 500 equivalents of the monomer to the polymer at room temperature within 360–720 min for rac-lactide and 10–30 min for ε-caprolactone. The formed polylactides are characterized by the atactic microstructure (Pr = 0.54–0.56) and polydispersity indices (PDI) of 1.6–2.5, whereas for polycaprolactone PDI = 2.1–2.8.

Publisher

The Russian Academy of Sciences

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