Solid‐state 31P and 109Ag 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)2L], [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 109Ag and 31P CPMAS NMR spectroscopy. 109Ag 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 109Ag chemical shifts and chemical shifts anisotropies. The silver chemical shift ranges for different P,S‐environments and coordination state were discussed in detail. The 1J(31P–107/109Ag) and 2J(31P–31P) values were determined and analyzed. A family of three‐ and four‐coordinated silver(I) complexes was probed by solid‐state 31P and 109Ag magic angle spinning NMR. 109Ag chemical shift ranges for different P,S‐environments and coordination state were defined.