The influence of the ligands on the catalytic activity of a series of Rh^I complexes in reactions with phenylacetylene: Synthesis of stereoregular poly(phenyl) acetylene

Abstract

Abstract The catalytic activity of a series of [Rh L‐L chel]X complexes, in which we have varied the unsaturated ligand [L‐L = cis, cis ‐cycloocta 1,5‐diene(cod) or 2,5‐norbornadiene(nbd) the nitrogen chelating ligand [chel = 2,2′‐bipyridine(bipy), 2,2′‐dipyridylamine(dipyam), 2,2′‐bipyrazine (bipz), 4,4′‐dimethyl‐2,2′‐bipyridine (4,4′‐Me 2 bipy)] and the counter ion [X = PF 6 , ClO 4 , BPh 4 ], has been examined in reactions with phyenylacetylene (PA). The catalytic behaviour of the [Rh(cod)Cl 2 ],tmeda (tmeda = N,N,N′,N′tetramethylethylendiamine), [Rh(cod)Cl 2 ],teda] (teda = triethylendiamine), of the dimer [Rh(cod)Cl] 2 , and the use of NaOH as cocatalyst in different reaction conditions was also examined. The influence of the ligands on the catalytic activity of these Rh I complexes is discussed. 1 H and 13 C NMR spectra have shown that highly stereoregular polyphenylacetilene can be obtained. Conditions for homogeneous doping of PPA, to obtain materials whose conductivity varies over 10–11 magnitude orders, are proposed. The stability of the doped polymers is also discussed.