Zinc complexes supported by maltolato ligands: synthesis, structure, solution behavior, and application in ring-opening polymerization of lactides
R Petrus, P Sobota - Organometallics, 2012 - ACS Publications
R Petrus, P Sobota
Organometallics, 2012•ACS PublicationsA series of novel zinc alkoxides supported by chelating maltolato (MalO; MalOH= maltol)
ligands were successfully synthesized and characterized. Reaction of MalOH with ZnEt2 (3:
4) gives a trinuclear cluster [Zn3 (Et) 2 (MalO) 4](1), which spontaneously disproportionates
in solution to mononuclear species [Zn (MalO) 2](1a) and [Zn (Et)(MalO)](1b);(1a) and (1b)
form [Zn (MalO) 2 (py)](2),[Zn (Et)(MalO)(py)](3),[Zn (MalO) 2] 2 ((1a) 2),[Zn (MalO)(OBn)] 2
((1c) 2), and [Zn4 (Et) 2 (OEt) 2 (MalO) 4](4) on addition of pyridine, benzyl alcohol (BnOH) …
ligands were successfully synthesized and characterized. Reaction of MalOH with ZnEt2 (3:
4) gives a trinuclear cluster [Zn3 (Et) 2 (MalO) 4](1), which spontaneously disproportionates
in solution to mononuclear species [Zn (MalO) 2](1a) and [Zn (Et)(MalO)](1b);(1a) and (1b)
form [Zn (MalO) 2 (py)](2),[Zn (Et)(MalO)(py)](3),[Zn (MalO) 2] 2 ((1a) 2),[Zn (MalO)(OBn)] 2
((1c) 2), and [Zn4 (Et) 2 (OEt) 2 (MalO) 4](4) on addition of pyridine, benzyl alcohol (BnOH) …
A series of novel zinc alkoxides supported by chelating maltolato (MalO; MalOH = maltol) ligands were successfully synthesized and characterized. Reaction of MalOH with ZnEt2 (3:4) gives a trinuclear cluster [Zn3(Et)2(MalO)4] (1), which spontaneously disproportionates in solution to mononuclear species [Zn(MalO)2] (1a) and [Zn(Et)(MalO)] (1b); (1a) and (1b) form [Zn(MalO)2(py)] (2), [Zn(Et)(MalO)(py)] (3), [Zn(MalO)2]2 ((1a)2), [Zn(MalO)(OBn)]2 ((1c)2), and [Zn4(Et)2(OEt)2(MalO)4] (4) on addition of pyridine, benzyl alcohol (BnOH), or dry O2, respectively. Compounds 1, 2, (1a)2, and 4 were characterized by elemental analysis, NMR, ESI-MS, and single-crystal X-ray structural analysis. Variable-temperature NMR experiments showed that (1a)2 and (1c)2 are in equilibrium with the monomeric form in solution. The addition of l-lactide (l-LA) to a combination of 1 and 2 equiv of BnOH in dichloromethane at room temperature in different molar ratios leads to rapid and efficient generation of poly(l-LA) with end-capped BnO groups. According to kinetic studies, propagation by [Zn(OBn)(MalO)] (1c) is first-order with respect to both the monomer and 1c concentrations; 1a in ring-opening polymerization of l-LA shows no activity. These results suggest a single-site active species in the ring-opening polymerization of l-LA.
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