Journal
CHEMICAL SCIENCE
Volume 6, Issue 9, Pages 5284-5292Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5sc01584g
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Funding
- NSERC Strategic Grant
- Green Centre Canada
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A methodology for controlling aggregation in highly active and isoselective indium catalysts for the ring opening polymerization of racemic lactide is reported. A series of racemic and enantiopure dinuclear indium ethoxide complexes bearing salen ligands [(ONNOR)InOEt](2) (R = Br, Me, admantyl, cumyl, t-Bu) were synthesized and fully characterized. Mononuclear analogues (ONNOR)InOCH(2)Pyr (R = Br, t-Bu, SiPh3) were synthesized by controlling aggregation with the use of chelating 2-pyridinemethoxide functionality. The nuclearity of metal complexes was confirmed using PGSE NMR spectroscopy. Detailed kinetic studies show a clear initiation period for these dinuclear catalysts, which is lacking in their mononuclear analogues. The polymerization behavior of analogous dinuclear and mononuclear compounds is identical and consistent with a mononuclear propagating species. The isotacticity of the resulting polymers was investigated using direct integration and peak deconvolution methodologies and the two were compared.
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