Synthesis and characterization of multi-alkali-metal tetraphenolates and application in ring-opening polymerization of lactide.
2012
A series of alkali metal complexes supported by two bulky tetraphenols were synthesized and characterized. The reactions of α,α,α′,α′-tetra(3,5-di-tert-butyl-2-hydroxyphenyl)-p-xylene(para-tetraphenol) with nBuLi, sodium, and KSi(NMe2)3 gave bimetallic complexes 1, 2, and 3, respectively. Treatments of the α,α,α′,α′-tetra(3,5-di-tert-butyl-2-hydroxyphenyl)-m-xylene(meta-tetraphenol) with 2 or 4 equiv of nBuLi afforded complexes 4 or 5, while the reactions of meta-tetraphenol with sodium and KSi(NMe2)3 gave only trimetallic complexes 6 and 7 for the additional p−π interaction. Complexes 1–7 were all characterized by single-crystal X-ray diffraction techniques. In the presence of benzyl alcohol, all complexes are active catalysts for the ring-opening polymerization of l-lactide. Comparatively, bimetallic complexes 1, 2, and 3 are more efficient catalysts because of their symmetric structures, in which complex 3 presents as a rare highly active potassium catalyst for the ring-opening polymerization of lactid...
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