C-C bond coupling between the organometallic cations CH3Ag2+, CH3Cu2+ and CH3AgCu+ and allyliodide

摘要

Electrospray ionisation on a mixture of AgNO3 ( in MeOH/H2O/acetic acid), (CH3CO2)(2)Cu ( in MeOH) and acetic acid ( in MeOH) yields the metal carboxylate cations CH3CO2Ag2+, CH3CO2AgCu+ and CH3CO2Cu2+. Collision induced dissociation of these carboxylate cations yields the organometallic cations CH3Ag2+, CH3AgCu+ and CH3Cu2+. The ion-molecule reactions of these organometallic cations with allyliodide were studied in a quadrupole ion trap mass spectrometer. C-C bond coupling occurred to yield the ionic products Ag2I+, AgCuI+ and Cu2I+. DFT calculations were carried out on these C-C bond coupling reactions. In all cases, the reactions are highly exothermic and involve initial coordination of the allyliodide to both metal atoms, with the iodine coordinating to one atom and the alkene moiety coordinating to the other. The overall mechanism of C-C bond coupling involves oxidative addition of the allyliodide followed by reductive elimination of 1-butene.