Journal of the American Chemical Society, 01 August 2012, Vol.134(30), pp.12758-73
A family of racemic and enantiopure indium complexes 1-11 bearing bulky chiral diaminoaryloxy ligands, H(NNO(R)), were synthesized and fully characterized. Investigation of both the mono- and the bis-alkoxy-bridged complexes [(NNO(R))InX](2)[μ-Y][μ-OEt] (5, R = (t)Bu, X = Y = Cl; 8, R = Me, X = I, Y = OEt) by variable temperature, 2D NOESY, and PGSE NMR spectroscopy confirmed dinuclear structures in solution analogous to those obtained by single-crystal X-ray crystallography. The dinuclear complexes in the family were highly active catalysts for the ring-opening polymerization (ROP) of lactide (LA) to form poly(lactic acid) (PLA) at room temperature. In particular, complex 5 showed living polymerization behavior over a large molecular weight range. A detailed investigation of catalyst stereoselectivity showed that, although (R,R/R,R)-5 is highly selective for l-LA, only atactic PLA is obtained in the polymerization of racemic LA. No such selectivity was observed for complex 8. Importantly, the selectivities obtained for the ROP of racemic LA with (R,R/R,R)-5 and (R,R/R,R)-8 are different and, along with kinetics investigations, suggest a dinuclear propagating species for these complexes.
Polymerization ; Coordination Complexes -- Chemistry ; Dioxanes -- Chemistry ; Indium -- Chemistry ; Lactic Acid -- Chemical Synthesis ; Polymers -- Chemical Synthesis
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