Kinetics of oxidative polymerization of 1,8‐nonadiyne

A study was made of the influence of the concentrations of catalyst, monomer, water, ligand, and oxygen on the rate of oxidative polymerization of 1,8‐nonadiyne (1) at 26°C in the presence of homogeneous catalysts derived from cuprous chloride (copper(I) chloride) and tertiary amines. In the initial stages the reaction is nearly first order in [Cu2Cl2] up to the solubility limit of the active catalyst, and second to first order in [1] for low to medium monomer concentrations. The reaction rate decreases with increasing water content and is enhanced by increasing ligand concentration and increasing basicity of the ligand: triethylamine (TEA) > N,N,N',N'‐tetramethylethylenediamine (TMED) > pyridine. On the basis of these kinetic results and a study of the catalyst structure a reaction scheme is proposed. In this scheme the formation of water occurs in reversible reaction steps from acetylenic endgroups and a dimeric copper(II) complex [TMED. Cu(OH)] · 2Cl−, followed by intramolecular oxidative coupling of two complexed acetylide ions.