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(PPh 3 ) 2 L], [Ag(PPh 3 )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, NH 2 ] 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.