Reactivity of Functionalized Vinyl Monomers in Insertion Copolymerization

We report the reactivities of a comprehensive range of polar vinyl comonomers and 1-olefins in the copolymerization with ethylene by [{(o-MeOC6H4)2­PC6H4SO3}­PdMe­(L)] from pressure reactor studies (95 °C, 3–20 bar), as defined by r E = k ethylene/k comonomer from Markov statistics. 13C NMR chemical shifts of the monomers’ β vinyl carbon atom and Charton and Sterimol parameters were found to be appropriate descriptors for the monomers’ electronic nature and steric demand, respectively. A comprehensive picture of their impact on monomer reactivity and also regioselectivity of insertion arises. This shall also allow for predictions of the reactivity of other monomers.