Copper(I) halide complexes with 2,2′-bis(diphenylphosphano)-1,1′-binaphthyl (rac-binap) and heterocyclic thiones. Racemic compounds in chiral and achiral crystal space groups

Reactions of copper(I) halides with racemic 2,2′-bis(diphenylphosphano)-1,1′-binaphthyl (rac-binap) in 1:1 molar ratio afforded mononuclear complexes of the type [CuX(rac-binap)] (X = Cl, Br, I) which, on further treatment with 1 equiv. of pyridine-2-thione (py2SH), pyrimidine-2-thione (pymtH) or 4,6-dimethyl-pyrimidine-2-thione (dmpymtH) gave rise to the formation of mixed-ligand complexes of the formula [CuX(rac-binap)(thione)]. The molecular structures of [CuBr(rac-binap)(py2SH)] · 2CH2Cl2, [CuBr(rac-binap)(py2SH)] · CH2Cl2 and [CuBr(rac-binap)(dmpymtH)] · CH2Cl2 have been established by single-crystal X-ray diffraction. Each of the complexes features a distorted tetrahedral copper(I) center with the phosphane acting in a chelating fashion. The complexes are strongly luminescent in the solid state at ambient temperature. Unusually, the [CuBr(rac-binap)(py2SH)] · 2CH2Cl2 molecules crystallise in a chiral space group with independent S- and R-enantiomers in the asymmetric unit.

Mixed-ligand complexes of the formula [CuX(binap)(thione)] are formed by the reaction between equimolar amounts of CuX, binap and a heterocyclic thione. The molecular structures of [CuBr(rac-binap)(py2SH)] · 2CH2Cl2, [CuBr(S-binap)(py2SH)] CH2Cl2 and [CuBr(S-binap)(dmpymtH)] CH2Cl2, established by single-crystal X-ray diffraction, feature a rigid distorted tetrahedral copper(I) center with the diphosphane acting in a chelating fashion. The complexes are strongly luminescent at room temperature in the solid state.Figure optionsDownload as PowerPoint slide