A DFT Study of R−X Bond Dissociation Enthalpies of Relevance to the Initiation Process of Atom Transfer Radical Polymerization

DFT calculations at the B3P86/6-31G** level have been carried out to derive the bond dissociation energies (BDE) and free energies for a number of R−X systems (X = Cl, Br, I, N 3, and S 2 CNMe 2 ) that have been or can potentially be used as initiators for atom transfer radical polymerization (ATRP). For selected systems, a conformational search was carried out for R−X and R by using semiempirical (PM3) and molecular mechanics (MM+ augmented with appropriately optimized parameters for the radical systems) methods. The MM+ technique is more suited to search for the most stable conformations. The computed energies are in good agreement with the experimentally available BDEs and reveal a small weakening effect caused by the substitution of an α-H atom with a CH 3 group. The free energies are used to derive the relative equilibrium constant for the ATRP activation/deactivation process. These are compared with the equilibrium constants that have been determined from ATRP polymerization rates and from model studies of activation−deactivation−termination processes in the absence of monomer. These comparisons reveal the effectiveness of the DFT-computed BDEs for predicting polymerization rates for new monomers in ATRP processes.