Quaternary onium modified SalenCoXY catalysts for alternating copolymerization of CO2 and propylene oxide: A kinetic study

Synthesis of Zn–Fe double metal cyanide complexes with imidazolium-based ionic liquid cocatalysts via ball milling for copolymerization of CO2 and propylene oxide

“…45,46 We inferred that the nucleophilic anion Y À accompanied with the loss of Y À via intramolecular nucleophilic substitution or cyclization of intermediate III. 47,48 Alternating copolymer polycarbonate V was formed by the further insertion of CO 2 and the activated PO molecule to ultimately yield the product PPC. The zinc complex and nucleophilic anion Y À of the IL work in cooperation with each other, which is essential to enable intramolecular synergistic action in copolymerization.…”

A New Dinuclear Cobalt Complex for Copolymerization of CO2 and Propylene Oxide: High Activity and Selectivity

“…Based on the above research, we proposed mechanisms for the dinuclear catalyst systems. In previous reports, a great deal of supported that CO 2 “insertion” actually occurs via a dissociative mechanism where a free nucleophilic chain end (alkoxide) attacks the CO 2 reversibly to give a carbonate end that is stabilized by the charge of the metal complex [ 16 , 37 , 41 , 48 , 49 , 50 , 51 ]. As shown in Figure 5 , first, the dinuclear complex interacted with the cocatalyst [PPN]Y to form two active centers ( I ), and the two active centers simultaneously activated the attacking PO to form a pair of hexacoordinate structures (intermediate II ).…”

Theoretical Study on Epoxide Ring-opening in CO2/Epoxide Copolymerization Catalyzed by Bifunctional Salen-Type Cobalt(III) Complexes: Influence of Stereoelectronic Factors

“…Desirably, the process is undergone in perfectly alternating fashion; in practice, divergence from the monomers' alternations often occurs, which is attributed to the experimental conditions or catalyst design [23]. As demonstrated by the experimental studies, the catalytic activity of binary and bifunctional systems appears to be affected by the structure of both the organometallic core and the cocatalyst salt [31,34,[36][37][38][39][40][41][42][43][44][45][46][47]. These findings, along with quantum-chemical studies (of rather limited number and dedicated mostly to less-computationally challenging binary catalysts) enabled a discussion of the various mechanistic aspects of CO 2 /epoxides copolymerization that can be found in the literature concerning cobalt(III)-based catalysts [17,21,41,[48][49][50][51][52].…”