Formation and reactions of the 1, 8-naphthyridine (napy) ligated geminally dimetallated phenyl complexes [(napy)Cu2(Ph)]+, [(napy)Ag2(Ph)]+ and [(napy)CuAg(Ph)]+

Gas-phase ion trap mass spectrometry experiments and density functional theory calculations have been used to examine the routes to the formation of the 1,8-naphthyridine (napy) ligated geminally dimetallated phenyl complexes [(napy)Cu₂(Ph)]⁺, [(napy)Ag₂(Ph)]⁺ and [(napy)CuAg(Ph)]⁺ via extrusion of CO₂ or SO₂ under collision-induced dissociation conditions from their corresponding precursor complexes [(napy)Cu₂(O₂CPh)]⁺, [(napy)Ag₂(O₂CPh)]⁺, [(napy)CuAg(O₂CPh)]⁺ and [(napy)Cu₂(O₂SPh)]⁺, [(napy)Ag₂(O₂SPh)]⁺, [(napy)CuAg(O₂SPh)]⁺. Desulfination was found to be more facile than decarboxylation. Density functional theory calculations reveal that extrusion proceeds via two transition states: TS1 enables isomerization of the O,O-bridged benzoate to its O-bound form; TS2 involves extrusion of CO₂ or SO₂ with the concomitant formation of the organometallic cation and has the highest barrier. Of all the organometallic cations, only [(napy)Cu₂(Ph)]⁺ reacts with water via hydrolysis to give [(napy)Cu₂(OH)]⁺, consistent with density functional theory calculations which show that hydrolysis proceeds via the initial formation of the adduct [(napy)Cu₂(Ph)(H₂O)]⁺ which then proceeds via TS3 in which the coordinated H₂O is deprotonated by the coordinated phenyl anion to give the product complex [(napy)Cu₂(OH)(C₆H₆)]⁺, which then loses benzene.