Reaction of the potassium salt of the N-thiophosphorylated thiourea Et 2NC(S)NHP(S)(OiPr) 2 (HL) with a mixture of AgNO 3 and PPh 3 in aqueous EtOH/CH 2Cl 2 leads to the mixed-ligand silver(I) complex [Ag(PPh 3) 2{Et 2NC(S)NP(S)(OiPr) 2}] ([Ag(PPh 3) 2L]). Recrystallization of [Ag(PPh 3) 2L] from an acetone/n-hexane mixture leads to the decomposition of the starting complex with the formation of [Ag(PPh 3){Et 2NC(S)NP(S)(OiPr) 2}] ([Ag(PPh 3)L]), [Ag(PPh 3) 3NCS]·(CH 3) 2C=O and Et 2NP(S)(OiPr) 2. The structures of [Ag(PPh 3) 2L], [Ag(PPh 3)L], [Ag(PPh 3) 3NCS]·(CH 3) 2C=O and Et 2NP(S)(OiPr) 2 were all investigated by IR, 31P{ 1H} and 1H NMR spectroscopy, and their compositions were established by elemental analysis. The crystal structure of the complex [Ag(PPh 3) 3NCS]·(CH 3) 2C=O obtained from single crystal X-ray diffraction is presented. © 2011 Elsevier B.V. All rights reserved.