Solid-state 31 P and 109 Ag CP/MAS NMR as a powerful tool for studying of silver(I) complexes with N-thiophosphorylated thiourea and thioamide ligands.

A family of three- and four-coordinated silver(I) complexes of formulas [Ag(PPh3 )2 L], [Ag(PPh3 )L], and [AgL]n with N-thiophosphorylated thiourea and thioamide ligands of general formula RC(S)NHP(S)(OPri)2 [R = Ph, PhNH, iPrNH, tBuNH, NH2 ] have been studied by solid-state 109 Ag and 31 P CPMAS NMR spectroscopy. 109 Ag NMR spectra have provided valuable structural information about Ag coordination, which is in good accordance with the available crystal structure data. The data presented in this work represent a significant addition to the available 109 Ag chemical shifts and chemical shifts anisotropies. The silver chemical shift ranges for different P,S-environments and coordination state were discussed in detail. The 1 J(31 P-107/109 Ag) and 2 J(31 P-31 P) values were determined and analyzed.

Complexes of N-thiophosphorylthioureas (HL) with copper(I). Crystal structures of [Cu3L3] and [Cu(PPh3)2L] chelates.

Reaction of the potassium salts of N-thiophosphorylated thioureas of common formula RC(S)NHP(S)(OiPr)(2) [R = morpholin-N-yl (HL(a)), piperidin-N-yl (HL(b)), NH(2) (HL(c)), PhCH(2)NH (HL(d))] with Cu(PPh(3))(3)I in aqueous EtOH/CH(2)Cl(2) leads to mononuclear [Cu(PPh(3))(2)L-S,S'] complexes. Using copper(i) iodide instead of Cu(PPh(3))(3)I, polynuclear complexes [Cu(n)(L-S,S')(n)] were obtained. The structures of these compounds were investigated by ES-MS, elemental analyses, 1H and 31P NMR in solution, IR and 31P solid-state MAS NMR spectroscopy. The crystal structures of [Cu(3)L(3)(a)] and [Cu(PPh(3))(2)L(b)] were determined by single-crystal X-ray diffraction.