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Synthesis and Structure of the (µ2-OP(O)Ph2)-Linked Dimeric Amide Lanthanum Complex {[\({\text{Pzl}}_{2}^{{{\text{Me2}}}}\)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

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Abstract

The dimeric amide lanthanum complex {[\({\text{Pzl}}_{{\text{2}}}^{{{\text{Me2}}}}\)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.

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ACKNOWLEDGMENTS

The workers of the Nesmeyanov Institute of Organoelement Compounds (Russian Academy of Sciences) are grateful to the Ministry of Science and Higher Education of the Russian Federation for financial support.

Funding

The XRD and NMR studies of the compounds were carried out using the equipment of the Center for Collective Use “Analytical Center of Institute of Organometallic Chemistry of Russian Academy of Sciences” and supported by the project “Provision of Development of Material Technical Infrastructure of Centers for Collective Use of Scientific Equipment” (unique identifier RF−2296.61321X0017, agreement no. 075-15-2021-670).

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Authors and Affiliations

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

    N. Yu. Rad’kova, A. V. Cherkasov & A. A. Trifonov

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

    A. A. Trifonov

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  1. N. Yu. Rad’kova
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  2. A. V. Cherkasov
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  3. A. A. Trifonov
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Correspondence to A. A. Trifonov.

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Translated by E. Yablonskaya

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Rad’kova, N.Y., Cherkasov, A.V. & Trifonov, A.A. Synthesis and Structure of the (µ2-OP(O)Ph2)-Linked Dimeric Amide Lanthanum Complex {[\({\text{Pzl}}_{2}^{{{\text{Me2}}}}\)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. Russ J Coord Chem 49, 710–717 (2023). https://doi.org/10.1134/S1070328423600717

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