Abstract
The mechanisms of H‐transfer in termination reactions, and the role of fluorine interactions to achieve the living polymerization of olefins, are investigated. Mecking's bis(enolatoimine)Ti catalysts are considered, with or without ortho‐F substituents. DFT calculations are performed on a parallel platform. The stationary structures are localized and energy barriers of activation are determined. Normal mode analysis is carried out and free energies are calculated. Different mechanisms can be involved in the termination: in all cases, the presence of F atoms rise the energy barrier of activation, according to experimental observations of living polymerization. The stabilizing role of the fluorine o‐F · · · H bonds in the equilibrium species, and destabilizing o‐F · · · H and o‐F · · · o‐F interactions in the transition states, are discussed.
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