Ligands, Lewis bases that coordinate to the metal center in a complex, can completely change the catalytic behavior of the metal center. In this Account, we summarize new reactions enabled by a single class of ligands, phosphine-sulfonates (ortho-phosphinobenzenesulfonates). Using their palladium complexes, we have developed four unusual reactions, and three of these have produced novel types of polymers.In one case, we have produced linear high-molecular weight polyethylene, a type of polymer that group 10 metal catalysts do not typically produce. Secondly, complexes using these ligands catalyzed the formation of linear poly(ethylene-co-polar vinyl monomers). Before the use of phosphine-sulfonate catalysts, researchers could only produce ethylene/polar monomer copolymers that have different branched structures rather than linear ones, depending on whether the polymers were produced by a radical polymerization or a group 10 metal catalyzed coordination polymerization. Thirdly, these phosphine-sulfonate catalysts produced nonalternating linear poly(ethylene-co-carbon monoxide). Radical polymerization gives ethylene-rich branched ethylene/CO copolymers copolymers. Prior to the use of phosphine-sulfonates, all of the metal catalyzed processes gave completely alternating ethylene/carbon monoxide copolymers. Finally, we produced poly(polar vinyl monomer-alt-carbon monoxide), a copolymerization of common polar monomers with carbon monoxide that had not been previously reported.Although researchers have often used symmetrical bidentate ligands such as diimines for the polymerization catalysis, phosphine-sulfonates are unsymmetrical, containing two nonequivalent donor units, a neutral phosphine, and an anionic sulfonate. We discuss the features that make this ligand unique. In order to understand all of the new reactions facilitated by this special ligand, we discuss both the steric effect of the bulky phosphines and electronic effects. We provide a unified interpretation of the unique reactivity by considering of the net charge and the enhanced back donation in the phosphine-sulfonate complexes.
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