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A Structurally Versatile Biguanide System for Possible Metal-Metal Cooperation in ROP of Cyclic Esters

Authors: Vlk Lukáš | Chlupatý Tomáš | Théron Benjamin | Breilly Damien | Růžičková Zdeňka | Malacea-Kabbara Raluca | Le Gendre Pierre | Růžička Aleš

Year: 2025

Type of publication: ostatní - přednáška nebo poster

Page from-to: nestránkováno

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Language	Name	Abstract	Keywords
eng	A Structurally Versatile Biguanide System for Possible Metal-Metal Cooperation in ROP of Cyclic Esters	Amidinates and guanidinates are well known capable ligands used for their electronic and steric flexibility and generally configurable properties.[1] The even more electron-rich skeleton of biguanides offers flexible moiety in regards of the geometry and π-electron density delocalization and thus supports multiple structural arrangements of its complexes.[2] These could act as bi-functional molecules and are prospective candidates for multi-metallic systems with possible advantages such as cooperative effect between the metals and electronic tuning.[3] In our group, we studied a hybrid biguanide-like guanidinate ligand able to mimic guanidinate and aza-β-diketiminate chelating coordination sites, which yields dianionic (hetero)bimetallic complexes. Several combinations of mostly main group (and post-transition metal) elements were explored with the ultimate aim of eventual utilization as catalytic species. An unexpected synthetic route opened the door for easy metal-substituent modification and, together with the possibility to influence a desired coordination pattern, allowed access to tailored purpose-built catalysts, tested in hydroelementation reactions and ring-opening polymerization (ROP) of cyclic esters. Some highly active and robust species were able to surpass turn-over frequencies of 60 000 h-1 in lactide ROP. Moreover, di- and triblock co-polymers of some combinations of lactide, ε-caprolactone or β-butyrolactone were obtained in immortal catalytic conditions. The story of development of this capable ligand platform as well as some results from ROP polymerization will be discussed.