Density functional calculations reveal that the stability of developing metal aryl bonds in Pd(II)-acetate C-H activation transition states determines regioselectivity in arene and heteroarene compounds. This kinetic-thermodynamic connection explains the general preference for activation of the strongest C-H bond and provides the possibility for regioselectivity prediction.
High-level ab initio molecular orbital calculations are used to study the magnitude and origin of the penultimate unit effect in atom transfer radical polymerization (ATRP) of dimers involving the co-monomers methyl acrylate (MA), methyl methacrylate (MMA) and propylene (P). The penultimate unit effects depend on the nature of the terminal unit and the halogen and can be significant, with the MMA unit in particular altering the equilibrium constant for the bond dissociation equilibrium by as much as 2 orders of magnitude.Specifically, the ratio of the equilibrium constants (K) for the bond dissociation reactions of H-M 2 -M 1 -Cl at 298 K, relative to the equilibrium constant (K 0 ) of the corresponding unimer
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