“…Silver(I) complex [Ag(diene) 2 ] þ Y À (where diene = cyclooctadiene, norbornadiene and 1,3-cyclohexadiene; Y À = PF 6 À , BF 4-) efficiently catalyses the arylation of N-tosylaziridines with arenes and heteroarenes under ambient conditions to provide the corresponding b-aryl amine derivatives with excellent regioselectivity. The following studies were conducted with the help of in situ NMR ( 1 H, 31 P, 109 Ag) and ESI-MS probe: (I) evaluation of Hammett reaction constant (r); (II) correlation of initial rate (k) vs. cone angle (y) of ligand L for reactions mediated by [Ag(COD) 2 ]PF 6 /L (where L is a phosphine or a phosphite ligand); (III) identification of silver-arene intermediates in solution; and (IV) correlation of initial rate (k) with DHOMO-LUMO of [Ag(diene) 2 ]PF 6 obtained from preliminary DFT studies. 148 High-resolution solid-state 109 Ag and 31 P NMR spectroscopy was used to study Ag dialkylphosphite salts, Ag(O)P(OR) 2 (R = CH 3 , C 2 H 5 , Bu and C 8 H 17 ), and determined whether they adopt keto, enol or dimer structures in the solid state.…”