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Macrocyclic Dizinc(II) Alkyl and Alkoxide Complexes: Reversible CO2 Uptake and Polymerization Catalysis Testing

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journal contribution
posted on 17.12.2015, 10:55 by Charles Romain, Michael S. Bennington, Andrew J. P. White, Charlotte K. Williams, Sally Brooker
The synthesis of three new dizinc­(II) complexes bearing a macrocyclic [2 + 2] Schiff base ligand is reported. The bis­(anilido)­tetraimine macrocycle reacts with diethylzinc to form a bis­(ethyl)­dizinc­(II) complex, [LEtZn2Et2] (1). The reaction of complex 1 with isopropyl alcohol is reported, forming a bis­(isopropyl alkoxide)­dizinc complex, [LEtZn2(iPrO)2] (2). Furthermore, complex 1, with 2 equiv of alcohol, is applied as an initiator for racemic lactide ring-opening polymerization. It shows moderately high activity, resulting in a pseudo-first-order rate coefficient of 9.8 × 10–3 min–1, with [LA] = 1 M and [initiator] = 5 mM at 25 °C and in a tetrahydrofuran solvent. Polymerization occurs with good control, as evidenced by the linear fit to a plot of molecular weight versus conversion, the narrow dispersities, and the limited transesterification. The same initiating system is inactive for the ring-opening copolymerization of carbon dioxide (CO2) and cyclohexene oxide at 80 °C and 1 bar of CO2 pressure. However, stoichiometric reactions between complex 2 and CO2, at 1 bar pressure, result in the reversible formation of new dizinc carbonate species, [LEtZn2(iPrO)­(iPrOCO2)] (3a) and [LEtZn2(iPrOCO2)2] (3b), and the reaction was studied using density functional theory calculations. All of the new complexes, 13b, are fully characterized, including NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction.