Sterically rigid bismuth pincer complexes; observation of the growing polymer chain in polar monomer polymerisation

A family of pyridine dipyrrolide bismuth complexes (^Mes,PhL)MX (1-6) (M = Bi, X = O-2,6-Me-C₆H₃ = OXyl (1); M = Sb, X = OXyl (2); M = Bi, X = O-2,6-Pr-C₆H₃ = ODipp (3), O-2,6-Bu-C₆H₃ = OAr (4), OBu (5) and OCMe₂Et = OAm (6), N(SiMe₃)₂ = N'' (7) and CH₂Ph (8)) have been prepared and investigated as initiators for the ring-opening polymerisation of lactide monomers. Bismuth lactate complexes (^Mes,PhL)Bi{OC(H)(Me)C(O)OR} were prepared as models for the propagating species (R = Bu (9), Me (10), Pr (11)). The first insertion of the lactide monomer is rate limiting and the second and subsequent insertions are more rapid (k_init ≪ k_LA2 < k_prop), leading to a significant induction period. The sterically demanding, rigid pincer ligand affords a well-defined coordination environment at the metal centre and allows for the enchainment of two lactide monomers to be differentiated spectroscopically ((^Mes,PhL)Bi{OC(H)(Me)C(O)}₄OX (12-X)), with this species also implied to be the true initiator for the regime of propagation with first order kinetics. Well-controlled first order kinetic data for the polymerisation of L-, D-, rac- and meso-lactide are observed.