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.

Two silver(I) complexes, [{Ag(SR)}₆][R¹SH = 6-(tert-butyldimethylsilyl)pyridine-2-thione 1, R²SH = 3,6-bis(tert-butyldimethylsilyl)pyridine-2-thione 2], have been synthesized by electrochemical oxidation of the metal in an acetonitrile solution of the neutral heterocyclic thiones. The reaction of equimolar amounts of dppm [bis(diphenylphosphino)methane] with complexes 1 and 2 in dichloromethane resulted in the formation of [Ag₄Cl₄(dppm)₂]3 and the elimination of RSCH₂SR. Single-crystal X-ray analyses were performed for compounds 1, 3 and R²SCH₂SR².