Development of Heterobimetallic Al/Mg Complexes for the Very Rapid Ring-Opening Polymerization of Lactides

[Image: see text] The successful architecture of active catalytic species with enhanced efficiencies is critical for the optimal exploitation of sustainable resources in industrially demanded processes. In this work, we describe the preparation of novel helical heterobimetallic Al/Mg-based complexes of the type [AlMe(2)(pbpamd(–))MgR{κ(1)-O-(OC(4)H(8)O)}] [R = Et (1a), (t)Bu (2a)] as potential catalysts. The design was performed through the sequential addition of the Al fragment to the ligand, followed by the Mg platform, resulting in a planar π-C(2)N(2)(sp(2))–Al/Mg bridging core between metals. The new heterobimetallic species have been unambiguously characterized by single-crystal X-ray analysis. NOESY, DOSY, and EXSY NMR studies as well as density functional theory calculations corroborate both a rearrangement in solution to scorpionate complexes containing an unprecedented apical carbanion with a direct σ-C(sp(3))–Al covalent bond named [{Mg(R)(pbpamd(–)) Al(Me)(2)}] [R = Et (1b), (t)Bu (2b)] and an interconversion equilibrium between both isomers. We verified their utility and high efficiency as catalysts in the well-controlled ring-opening polymerization of the biorenewable l- and rac-lactide (LA) at 23 °C, reaching a remarkable turnover frequency value close to 25000 h(–1) for rac-LA at this temperature and exerting a significant level of heteroselectivity (P(r) = 0.80). Very interestingly, the kinetics demonstrate apparent first-order with respect to the catalyst and LA, which supports a synergic intramolecular cooperation between centers with electronic modulation among them.