The monomer 5-ethynyl-NN-dimethylnaphthalen-1-amine (2) was satisfactorily obtained by a heterocoupling reaction between 5-iodo-(N,N-dimethyl)naphthalen-l-amine and 2-methyl-3-butyn-2-ol catalyzed by a palladium-copper system and followed by acetone elimination. Poly(5-ethynyl-N,N-dimethylnaphthalen-1-amine) was isolated by the reaction of 2 in the presence of homogeneous rhodium and palladium complexes. On the basis of the spectroscopic data, the polymer always showed a cis-transoidal, stereoregular structure. Moreover, only with the rhodium catalyst in methanol was a dimeric product isolated in a very low yield, having a conjugated terminal ene-yne structure, which permitted the consideration of a metallated chain-transfer intermediate in the polymer propagation. The kinetics of the catalyzed reaction were analyzed. (c) 2006 Wiley Periodicals, Inc.