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Ring-Opening Polymerization of Lactide and Ring-Opening Copolymerization of Cyclohexene Oxide and Phthalic Anhydride by Multinuclear Complexes of Zinc; Magnesium and Potassium
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DOI：10.1039/D6NJ01550F.png)
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Abstract
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The synthesis and structural characterization of multinuclear complexes containing amino-bis(phenolate) ligands with zinc and magnesium centres are reported. Trimetallic zinc complex Zn2(Zn(OAc)2)[L]2 (1) (where [L] = dimethylaminoethylamino-N; N-bis(2-methylene-4-methyl-6-methoxyphenolate)) was reacted with magnesium acetate in methanol to form a heterometallic complex; Zn2(Mg(OAc)2)[L]2 with different levels of occupancy at the central metal site depending on the reaction conditions used. Addition of methanolic solutions of Mg(OAc)2 at –78 °C and warming to room temperature gave a complex with 74% of the central zinc positions replaced with magnesium (2). Heating the methanolic solution to reflux resulted in a higher displacement of the central zinc positions; giving 94% occupancy of the central metal site by magnesium (3). A multimetallic complex containing three Zn(II) centres and four K(I) centres; two L ligands; and six acetate co-ligands; {[LZn(OAc)]2Zn(KOAc)4} (4); was also synthesized and characterized. Complexes 1 and 3 catalyze the ring-opening polymerization (ROP) of rac-lactide (rac-LA); giving polyesters with and without the presence of benzyl alcohol (BnOH) as a co-catalyst. Complexes 1 and 3 also catalyze ring-opening copolymerization (ROCOP) of cyclohexene oxide (CHO) and phthalic anhydride (PA); giving moderate molar mass polymers with narrow dispersities.
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