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Abstract : Abstract The benzene, CO, and {PPh3} adducts [HB(3-(CF3),5-(Ph)Pz)3]AgL (L = C6H6, CO, or PPh3) have been synthesized by a metathesis process using [HB(3-(CF3),5-(Ph)Pz)3]Na(THF), CF3SO3Ag, and the corresponding co-ligands. These silver(I) adducts have been characterized by {NMR} spectroscopy, and by X-ray crystallography. In all cases the Scorpionate is bound to silver in typical κ3-fashion. The X-ray crystallographic data of [HB(3-(CF3),5-(Ph)Pz)3]Ag(η2-C6H6) show that it has a η2-bound benzene molecule. {NMR} data point to fluxional behavior in solution. The 13C {NMR} resonance corresponding to the {CO} moiety of [HB(3-(CF3),5-(Ph)Pz)3]Ag(CO) appears as a single peak at δ 177.4 ppm and the ν ¯ co is observed at 2148 cm−1. These values indicate the presence of a fairly Lewis acidic silver atom in [HB(3-(CF3),5-(Ph)Pz)3]Ag(CO) and significantly diminished Ag → {CO} π-backbonding. Interesting coupling is observed in the solution 19F and 31P {NMR} spectra of the Ag(I) adduct [HB(3-(CF3),5-(Ph)Pz)3]Ag(PPh3). A detailed analysis of the spectral and structural features of these complexes has been described herein