Tetraalkylcuprates(III): formation, association, and intrinsic reactivity

Tetraalkylcuprates are prototypical examples of organocopper(III) species, which remained elusive until their recent detection by NMR spectroscopy. In agreement with the NMR studies, the present electrospray ionization mass spectrometric experiments, as well as supporting electrical conductivity measurements, indicate that LiCuMe(2)·LiCN reacts with a series of alkyl halides RX. The resulting Li(+)Me(2)CuR(CN)(-) intermediates then afford the observable Me(3)CuR(-) tetraalkylcuprate anions upon Me/CN exchanges with added MeLi. In contrast, the reactions of LiCuMe(2)·LiCN with neopentyl iodide and various aryl halides give rise to halogen-copper exchanges. Concentration- and solvent-dependent studies suggest that lithium tetraalkylcuprates are not fully dissociated in ethereal solvents, but partly form Li(+)Me(3)CuR(-) contact ion pairs and presumably also triple ions LiMe(6)Cu(2)R(2)(-). According to theoretical calculations, these triple ions consist of two square-planar Me(3)CuR(-) subunits binding to a central Li(+) ion. Upon fragmentation in the gas phase, the mass-selected Me(3)CuR(-) anions undergo reductive elimination, yielding both the cross-coupling products MeR and the homocoupling product Me(2). The branching between these two fragmentation channels markedly depends on the nature of the alkyl substituent R. The triple ions LiMe(6)Cu(2)R(2)(-) (as well as their mixed analogues LiMe(6)Cu(2)R(R')(-)) also afford both cross-coupling and homocoupling products upon fragmentation, but strongly favor the former. On the basis of theoretical calculations, we rationalize this prevalence of cross-coupling by the preferential interaction of the central Li(+) ion of the triple ions with two Me groups of each Me(3)CuR(-) subunit, which thereby effectively blocks the homocoupling channel. Our results thus show how a Li(+) counterion can alter the reactivity of an organocopper species at the molecular level.