High
-resolution solid-state 109 Ag and 31 P NMR spectroscopy was used to investigate a series of silver dialkylphosphite salts, Ag(O)P(OR) 2 (R = CH 3 , C 2 H 5 , C 4 H 9 and C 8 H 17 ), and determine whether they adopt keto, enol or dimer structures in the solid state. The silver chemical shift, CS, tensors and |J( 109 Ag, 31 P)| values for these salts were determined using 109 Ag ( = 4.652%) NMR spectroscopy. The magnitudes of J( 109 Ag, 31 P) range from 1250 Β± 10 to 1318 Β± 10 Hz and are the largest reported so far. These values indicate that phosphorus is directly bonded to silver for all these salts and thus exclude the enol structure. All 31 P NMR spectra exhibit splittings due to indirect spin-spin coupling to 107 Ag (I = 1/2, NA = 51.8%) and 109 Ag (I = 1/2, NA = 48.2%). The 1 J( 109 Ag, 31 P) values measured by both 109 Ag and 31 P NMR spectroscopy agree within experimental error. Analysis of 31 P NMR spectra of stationary samples for these salts allowed the determination of the phosphorus CS tensors. The absence of characteristic P O stretching absorption bands near 1250 cm -1 in the IR spectra for these salts exclude the simple keto tautomer. Thus, the combination of solid-state NMR and IR results indicate that these silver dialkylphosphite salts probably have a dimer structure. Values of silver and phosphorus CS tensors as well as 1 J( 109 Ag, 31 P) values for a dimer model calculated using the density functional theory (DFT) method are in agreement with the experimental observations.