Formation and reactions of the 1, 8-naphthyridine (napy) ligated geminally dimetallated phenyl complexes [(napy)Cu(Ph)], [(napy)Ag(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)Cu(Ph)], [(napy)Ag(Ph)] and [(napy)CuAg(Ph)] via extrusion of CO or SO under collision-induced dissociation conditions from their corresponding precursor complexes [(napy)Cu(OCPh)], [(napy)Ag(OCPh)], [(napy)CuAg(OCPh)] and [(napy)Cu(OSPh)], [(napy)Ag(OSPh)], [(napy)CuAg(OSPh)]. 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 CO or SO with the concomitant formation of the organometallic cation and has the highest barrier. Of all the organometallic cations, only [(napy)Cu(Ph)] reacts with water via hydrolysis to give [(napy)Cu(OH)], consistent with density functional theory calculations which show that hydrolysis proceeds via the initial formation of the adduct [(napy)Cu(Ph)(HO)] which then proceeds via TS3 in which the coordinated HO is deprotonated by the coordinated phenyl anion to give the product complex [(napy)Cu(OH)(CH)], which then loses benzene.