C-C bond coupling between the organometallic cations CH3Ag2+, CH3Cu2+ and CH3AgCu+ and allyliodide.
Electrospray ionisation on a mixture of AgNO(3) (in MeOH/H(2)O/acetic acid), (CH(3)CO(2))(2)Cu (in MeOH) and acetic acid (in MeOH) yields the metal carboxylate cations CH(3)CO(2)Ag(2)(+), CH(3)CO(2)AgCu(+) and CH(3)CO(2)Cu(2)(+). Collision induced dissociation of these carboxylate cations yields the organometallic cations CH(3)Ag(2)(+), CH(3)AgCu(+) and CH(3)Cu(2)(+). 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 Ag(2)I(+), AgCuI(+) and Cu(2)I(+). 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.
Khairallah
George N
GN
School of Chemistry, University of Melbourne, Victoria 3010, Australia.
Waters
Tom
T
O'Hair
Richard A J
RA