Mixed-ligand complexes of copper(I) with diimines and phosphines: Effective catalysts for the coupling of phenylacetylene with halobenzene

New copper(I) mixed-ligand complexes 1–4 of the formula Cu(N–N)PR3X, where N–N = 1,10-phenanthroline (phen), 2,2′-bipyridine (bpy), 5,5′-dimethyl-2,2′-bipyridine (5,5′dimbpy) and PR3 = tricyclohexylphosphine, tris(2-cyanoethyl)phosphine and isopropyldiphenylphosphine, have been synthesized. The complexes were characterized by EA, IR, NMR and single crystal X-ray diffraction. The solution fluorescence emission spectra were measured. The single crystal X-ray analysis showed that the copper(I) ion is four-coordinate with a distorted tetrahedral geometry. The complexes catalyze the formation of diphenylacetylene from the coupling of halobenzene with phenylacetylene. The complex Cu(5,5′-dimethylbpy)P{(cyhexyl)3}I showed the highest catalytic activity. At room temperature all four complexes exhibit, in dichloromethane, emission maxima in the 329–344 nm range, corresponding to intra-ligand excited states.

Graphical abstractNew copper(I) mixed-ligand complexes of the formula Cu(N–N)PR3X have been synthesized and characterized. The copper(I) ion is four-coordinate with a distorted tetrahedral geometry. The complexes catalyze the formation of diphenylacetylene from the coupling of halobenzene with phenylacetylene.Figure optionsDownload full-size imageDownload as PowerPoint slide