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Issue 13, 2012
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Ring-opening polymerisation of rac-lactide mediated by cationic zinc complexes featuring P-stereogenic bisphosphinimine ligands

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Abstract

The diastereomerically pure P-stereogenic bis(phosphinimine) ligands 4,6-(ArN[double bond, length as m-dash]PMePh)2dbf [Ar = 4-isopropylphenyl (Pipp): rac-4, meso-4; Ar = 2,6-diisopropylphenyl (Dipp): rac-4a; dbf = dibenzofuran] were synthesised and complexed to zinc using a protonation-alkane elimination strategy. The cationic alkylzinc complexes thus obtained, RZn[4,6-(ArN[double bond, length as m-dash]PMePh)2dbf][B(Ar′)4] [Ar = Pipp, Ar′ = C6H3(CF3)2: rac-6 (R = Et), meso-6 (R = Et), rac-7 (R = Me) meso-7 (R = Me); Ar = Dipp: rac-6a (R = Et, Ar′ = C6H3(CF3)2), rac-6b (R = Et, Ar′ = C6F5)] were investigated for their competency as initiators for the ring-opening polymerisation of rac-lactide. The formation of polylactide was achieved under relatively mild conditions (40 °C, 2–4 h) and the microstructures of the resulting polymers exhibited a slight heterotactic bias [polymer tacticity (Pr) = 0.51–0.63].

Graphical abstract: Ring-opening polymerisation of rac-lactide mediated by cationic zinc complexes featuring P-stereogenic bisphosphinimine ligands

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Publication details

The article was received on 17 Oct 2011, accepted on 19 Dec 2011 and first published on 15 Feb 2012


Article type: Paper
DOI: 10.1039/C2DT11954D
Citation: Dalton Trans., 2012,41, 3701-3713
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    Ring-opening polymerisation of rac-lactide mediated by cationic zinc complexes featuring P-stereogenic bisphosphinimine ligands

    H. Sun, J. S. Ritch and P. G. Hayes, Dalton Trans., 2012, 41, 3701
    DOI: 10.1039/C2DT11954D

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