Journal
INORGANIC CHEMISTRY
Volume 54, Issue 24, Pages 11842-11851Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.5b02038
Keywords
-
Categories
Funding
- University of Otago
- MacDiarmid Institute for Advanced Materials and Nanotechnology
- EPSRC [EP/EP/L017393/1, EP/K035274, EP/K014070/1]
- EPSRC [EP/K035274/1, EP/K014676/1, EP/L017393/1, EP/K039946/1, EP/K014668/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/K014668/1, EP/K035274/1, EP/K039946/1, EP/K014676/1, EP/C544838/1, EP/L017393/1] Funding Source: researchfish
Ask authors/readers for more resources
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 x 10(-3) min(-1), with [LA] = 1 M and [initiator] = 5 mM at 25 degrees 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 degrees 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)(iPrOCO(2))] (3a) and [LEtZn2(iPrOCO(2))(2)] (3b), and the reaction was studied using density functional theory calculations. All of the new complexes, 1-3b, are fully characterized, including NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available