Exploring the conformational space of cobalt(III)-salen catalyst for CO 2 /epoxide copolymerization: Effect of quaternary ammonium salts on preference of alternative isomers.

Model catalysts for CO2 /epoxide copolymerization based on Co(III) complexes were studied, with focus on the preference of their alternative isomers, cisβ vs. trans. The systems range from model structures without the co-catalyst, as derived from crystallographic data, to complex models with two (CH2 )4 N+ R3 co-catalyst chains (R = Me, Bu) grafted onto a Co(III)-salcy core. To explore the conformational space of the latter complexes, a computational protocol was developed, combining a systematic model-building approach with static and molecular dynamics calculations, and multilevel energy assessment (PM7 and DFT). Results demonstrate an influence of the co-catalyst on the relative stability of the isomers. The cisβ isomer is preferred for complexes without N+ -chains and the cisβ ↔ trans isomerization is feasible. Five-coordinate species and open-shell electronic configurations are energetically disfavored. The cisβ preference decreases with the introduction and enlargement of (CH2 )4 N+ R3 : both isomers can be populated for R = Me, while the trans isomer is visibly preferred for R = Bu. © 2018 Wiley Periodicals, Inc.