Intermolecular hydroamination versus stereoregular polymerization of phenylacetylene by rhodium catalysts based on N–O bidentate ligands

N–O bidentate ligands, such as 8-quinolinol and aminoacids, in combination with the dinuclear precursor [{Rh(μ-OMe)(COD)}2] are versatile catalytic systems. Thus, stereoregular polymerization of phenylacetylene (PA) is observed in the presence of secondary amines. Interestingly, the outcome of the catalysis changes drastically on addition of strong coordinating phosphines, giving the product of the intermolecular anti-Markovnikov hydroamination of phenylacetylene.