The electrochemical oxidation of anodic metal (cobalt, nickel, copper and silver) in acetonitrile solutions of the appropriate heterocyclic thione, RMe₂SipySH (3-Bu^tMe₂SipySH, 3-ThexMe₂SipySH, 6-ThexMe₂SipySH) gave complexes of general formula [M(RMe₂SipyS)] (M = Cu, Ag) and [M(RMe₂SipyS)_n] (when M = Co, n = 3; M = Ni, n = 2). When the oxidation was repeated in the presence of 2,2′-bipyridine (bipy), the mixed complexes [M(RMe₂SipyS)₂(bipy)] were obtained only in the case of M = Ni. The reaction between copper complexes, [M(RMe₂SipyS)], and 1,2-bis(diphenylphosphino)ethane (dppe) and bis(diphenylphosphino)methane (dppm) in acetonitrile yielded [Cu₂(RMe₂SipyS)₂(dppe)₃] and [Cu₂(RMe₂SipyS)₂(dppm)₂]. The molecular structures of [Cu₆(3-Bu^tMe₂SipyS)₆], 1, [Cu₆(6-ThexMe₂SipyS)₆], 2, and [3-Bu^tMe₂SipyS-Spy-3-Bu^tSiMe₂], 3, were determined by X-ray diffraction. Compounds 1 and 2 are hexanuclear with the six copper atoms arranged in a distorted octahedral geometry and each copper atom in a distorted trigonal planar [CuS₂N] environment, each ligand adopting the N,S-bidentate S-bridging mode. The electronic, vibrational and ¹H and ¹³C NMR spectra of the complexes are discussed and related to the structure.