salicylates and dilactide

Two novel zinc alkoxides supported by chelating methyl salicylato (MesalO; MesalOH = methyl salicylate) ligands were successfully synthesized and characterized. Reaction of MesalOH with ZnEt2 (2:1) gives a tetranuclear cluster [Zn(MesalO)2]4 (1), which by addition of pyridine is transformed to the mononuclear compound [Zn(MesalO)2(py)2] (2). Compounds 1 and 2 were characterized by elemental analysis, NMR, IR, and single crystal X-ray diffraction. The catalytic activity of both compounds was tested for the ring-opening polymerization (ROP) of L-lactide (L-LA). It was found that compounds 1 and 2 are efficient initiators of the ROP of L-LA, yielding cyclic PLLA with weight average molecular weights up to 100 kDa for 2. The treatment of 2 with 1 equiv. of BnOH in toluene afforded a dimeric compound [Zn(OBn)(MesalO)(py)]2 (3). The addition of L-LA to a combination of 1 and 4 equiv. of BnOH in THF or 2 and 1 equiv. of BnOH in toluene led to the rapid and efficient generation of PLLA with end-capped BnO groups.

Topics: Catalysis; Crystallography, X-Ray; Dioxanes; Magnetic Resonance Spectroscopy; Models, Molecular; Organometallic Compounds; Polyesters; Polymerization; Pyridines; Salicylates; Spectrometry, Mass, Electrospray Ionization; Spectrophotometry, Infrared; Zinc

Salen bismuth alkoxides, where the salen ligand contains 2,4-di-tert-butylphenoxy groups and one of ethylene, cyclohexane or ortho-phenyl as a backbone have been prepared from reactions involving Bi[N(SiMe₃)₂]₃ and the free salen ligand followed by alcoholysis (ButOH, PriOH and 2,6-But₂C₆H₃OH). The molecular structures of the salen ligand with the cyclohexyl back-bone have been determined for the complexes salenBiCl and salenBiOC₆H₃-2,6-But₂. The chloro compound is a dimer with chloride bridges while the phenoxide is monomeric with an unusually distorted five-coordinate geometry. The phenoxide and tert-butoxide complexes have been employed in the ring-opening polymerization of lactides (L- and rac-) to give polylactides, PLAs. With rac-LA heterotactic PLA is formed preferentially, Pr = ~0.9, in dichloromethane or toluene at room temperature. The reaction is first order in [Bi] and is notably faster than most aluminum and zinc initiators as well as tin(II) octanoate. These results are discussed in terms of a recent report on the polymerization of LA by Peptobismol® and bismuth subsalicylate.

Topics: Bismuth; Catalysis; Coordination Complexes; Crystallography, X-Ray; Dioxanes; Ethylenediamines; Kinetics; Molecular Conformation; Organometallic Compounds; Polyesters; Salicylates