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Overcoming aggregation in indium salen catalysts for isoselective lactide polymerization.


ABSTRACT: 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)InOCH2Pyr (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.

SUBMITTER: Aluthge DC 

PROVIDER: S-EPMC5669251 | biostudies-literature | 2015 Sep

REPOSITORIES: biostudies-literature

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Overcoming aggregation in indium salen catalysts for isoselective lactide polymerization.

Aluthge D C DC   Ahn J M JM   Mehrkhodavandi P P  

Chemical science 20150706 9


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 [(ONNO<sub>R</sub>)InOEt]<sub>2</sub> (R = Br, Me, admantyl, cumyl, <i>t</i>-Bu) were synthesized and fully characterized. Mononuclear analogues (ONNO<sub>R</sub>)InOCH<sub>2</sub>Pyr (R = Br, <i>t</i>-Bu, SiPh<sub>3</sub>) were synthesized by c  ...[more]

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