The “frustrated Lewis pair” (FLP) chemistry [1] has stimulated chemists’ imagination and thus promoted an explosive level of interest since the seminal works [2] of Stephan and Erker, which introduced the FLP concept to describe sterically encumbered Lewis acid (LA, like Al(C6F5)3) and Lewis base (LB, e.g., PtBu3) pairs that are sterically precluded from forming classical donor–acceptor adducts. Instead, the opposite reactivity of the unquenched LA and LB of a FLP can promote unusual reactions, or reactions that were previously known to be promoted only by transition-metal complexes, such as activation of H2, CO2, N2O, B-H bonds, alkenes and alkynes, as well as catalytic hydrogenation. Here we present a summary of theoretical investigations into the recently discovered catalytic reactivity promoted by FLPs [3] (see Chart 1) in the polymerization of conjugated polar alkenes such as methyl methacrylate (MMA). Computational studies on the active species formation as well as on the chain initiation and propagation events involved have lead a deep understanding of the fundamental steps of the polymerization process. Moreover, the computational results have brought to light the favored termination mechanism [4] between the two competitive pathways, goal that couldn’t be reached by only experimental efforts. Chart 1 [1] For recent reviews, see: (a) D. W. Stephan, G. Erker, Angew. Chem. Int. Ed. 2010, 49, 46−76; (b) G. Erker, Dalton Trans. 2011, 40, 7475−7483. [2] (a) J. S. J. McCahill, G. C. Welch, D. W. Stephan, Angew. Chem. Int. Ed. 2007, 46, 4968−4971; (b) P. A. Chase, G. C. Welch, T. Jurca, D. W. Stephan, Angew. Chem. Int. Ed. 2007, 46, 8050−8053. [3] Y. Zhang , G.M. Miyake, M. G. John, L. Falivene, L. Caporaso, L. Cavallo, E. Y.-X., “Lewis pair polymerization by classical and frustrated Lewis pairs: acid, base and monomer scope and polymerization mechanism” , Dalton Trans., 41(2012), pp 9119-9134. [4] H. Jianghua, Y. Zhang, L. Falivene, L. Caporaso, L. Cavallo, E. Y.-X. Chen, Propagation Kinetics and Chain Termination in Polymerization of Conjugated Polar Alkenes by [Al]-based Frustrated Lewis Pairs, submitted

Methyl methacrylate Polymerization by Frustrated Lewis Pairs (FLPs): Polymerization and termination Mechanism

249th National Meeting (2015)

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