Copper(I) complexes with 4,6-dimethylpyrimidine-2-thione (Hdmpymt); the crystal and molecular structure of [Cu6(dmpymt)6]

Abstract

The complex [Cu₆(dmpymt)₆]·H₂O was synthesised by electrochemical oxidation of copper in an acetonitrile solution of the neutral ligand 4,6-dimethylpyrimidine-2-thione (Hdmpymt). The reaction of [Cu₆(dmpymt)₆] with 1,2-bis(diphenylphosphino)methane (dppm) and 1,2-bis(diphenylphosphino)ethane (dppe) yielded compounds of general formulae [Cu(dmpymt)(dppm)] and [Cu₂(dmpymt)₂(dppe)₃]. The molecular structure of [Cu₆(dmpymt)₆] was determined: the crystals are triclinic, space group P1, a= 11.432(3), b= 13.395(2), c= 15.694(4)Å, α= 80.28(2), β= 87.75(2), γ= 73.87(2)° and Z= 2. The six copper atoms are arranged with distorted-octahedral geometry, each copper atom being trigonally co-ordinated to one nitrogen and two sulfur atoms of three different ligands. Infrared, ¹H, ¹³C and ³¹P NMR spectral data are presented for all the compounds.