Comparison of Imine- and Phosphinimine-Supported Indium Complexes: Tuning the Reactivity for the Sequential and Simultaneous Copolymerization of Lactide and ε-Caprolactone.

Imine- and phosphinimine-supported indium complexes were used as catalysts in the polymerization of racemic lactide and ε-caprolactone as well as their copolymerization by the sequential and simultaneous addition of monomers. Tuning the electronics and sterics of the indium centers by either (i) changing the nature of the nitrogen donors and (ii) coordinating a hemilabile side group had a significant effect on the reactivity of the complexes, their stability, and their control in the synthesis of block copolymers. Specifically, the imine-supported complex (5) showed the highest activity in the homo- and copolymerization of the cyclic esters, in contrast to the phosphinimine-supported complex (7), which was significantly slower and less stable. The presence of morpholine and thiomorpholine hemilabile side groups either reduced the activity or prevented the formation of alkoxide complexes.