Polymerization of Terminal Acetylenes by a Bulky Monophosphine-Palladium Catalyst

A well-defined palladium complex [(tBuXPhos)­Pd­(Me)­(BArf)] bearing a bulky monophosphine ligand was synthesized and fully characterized. X-ray diffraction analysis shows that the 1,3,5-triisopropylaryl group of the dialkylbiaryl phosphine ligand exhibits a weak η6-interaction with the Pd­(II) center. This catalyst exhibits excellent functional group tolerance and polymerizes propargyl esters containing benzoyl and acetyl groups, propargyl methyl ether, propargyl alcohol, benzyl acetylene, and phenyl acetylene to yield polymers with Mn values in the range of 5–15 kDa with monomodal molecular weight distributions between ca. 1.4 and 2.1.