Heteroleptic Cu(I) and Ag(I) complexes of N-thiophosphorylated tris–thioureas and triphenylphosphane

Abstract

The reaction between tris(2-aminoethyl)amine or diethylenetriamine and O,O′-diisopropyl-isothiocyantothiophosphate (iPrO)2P(S)NCS gives the tris–functional thioureas N(CH2CH2NHC(S)NHP(S)(OiPr)2)3 (H3LI) and N(C(S)NHP(S)(OiPr)2)(CH2CH2NHC(S)NHP(S)(OiPr)2)2 (H3LII) with three C(S)NHP(S)(OiPr)2 groups. The reaction of the potassium salts K3LI,II with a mixture of CuI or AgNO3 and PPh3 in aqueous EtOH/CH2Cl2 leads to the [M3(PPh3)6LI,II] complexes. According to the IR, 1H and 31P{1H} NMR data, the deprotonated thioureas LI,II are coordinated through the sulfur atoms of the thiocarbonyl and thiophosphoryl groups in [M3(PPh3)6LI,II], both in the solid state and in solution. The complexes [Cu3(PPh3)6LI,II] and [Ag3(PPh3)6LI,II] show emissions in the solid state at about 465 and 490nm, respectively.