Initiation of ring-opening polymerization of lactide: The effect of metal alkoxide catalyst

► Computations reveal the mode of action of six metal alkoxide catalysts on the initiation stage of the ROP of m-lactide. ► The influence of tetrahydrofuran medium is simulated. ► For all studied catalysts the rate controlling stages are associated with rearrangements preceding ring cleavage. ► The catalytic activity is rationalized in terms of electronic structure parameters.