Polynuclear and mixed-ligand mononuclear CuI complexes with N-thiophosphorylated thioureas and 1,10-phenanthroline or PPh3

Abstract

Deprotonation of the N-thiophosphorylated thioureas RC(S)NHP(S)(OiPr)₂ (R = Me₂N, HL^I; iPrNH, HL^II; 2,6-Me₂C₆H₃NH, HL^III, 2,4,6-Me₃C₆H₂NH, HL^IV, aza-15-crown-5, HL^V) and reaction with CuI or Cu(NO₃)₂ in aqueous EtOH leads to the polynuclear complexes [Cu₄(L^I–S,S′)₄], [Cu₈(L^II–S,S′)₈], and [Cu₃(L^III–V–S,S′)₃]. The structures of these compounds were investigated by IR, ¹H, ³¹P{¹H} NMR, UV-vis spectroscopy and elemental analyses. The crystal structures of [Cu₄L^I₄], [Cu₈L^II₈], [Cu₃L^III,IV₃] were determined by single-crystal X-ray diffraction. Reaction of the deprotonated ligands (L^I–V)⁻ with a mixture of CuI and 1,10-phenanthroline (phen) or PPh₃ leads to the mixed-ligand mononuclear complexes [Cu(phen)L^I–V], [Cu(PPh₃)L^I–V] or [Cu(PPh₃)₂L^I–V]. The same mixed-ligand complexes were obtained from the reaction of [Cu₄L^I₄], [Cu₈L^II₈], [Cu₃L^III–V₃] with phen or PPh₃.