Combining oxidative addition and polymerization: A study towards the synthesis of macromonomers

Abstract

Oxidative addition to a metal in a low valent state produces catalysts that allow reporter or functional groups to be introduced to a polymer chain end. Substituted allyltrifluoroacetates were added to Ni(0)(COD)₂. The resulting π-allyl-Ni trifluoroacetates are dimeric in the solid state as well as in solution. The crystal structure of bis[(η³-2-phenylallyl)(trifluoroacetato)-nickel(II)], bis[(η³-2-trimethylsilylallyl)(trifluoroacetato)nickel(II)], are given and correlated with the reactivity as polymerization catalysts. Butadiene, styrene, and norbornene are used as monomers. The substituent of the allyl group is found quantitatively to be the end group of each macromolecule. Thus it is demonstrated that no chain transfer occurs.