C-C Bonding in Molecular Systems via Cross-Coupling-like Reactions Involving Noncovalently Bound Constituent Ions

Carbon-based molecules are of universal importance for a huge variety of chemical and biological processes. The complication of the structure of such molecules proceeds via the bonding of carbon atoms. An efficient mechanism for such reactions proceeds via cross-coupling, related to the association of bond-terminating counter-ions. Here, an uncommon version of such a process is investigated, with at least some ions bound in the system noncovalently and/or switching the bonding mode in due course. The analyzed sample reactions involve a single C-C bond formation in environmentally relevant halocarbon species and involve alkali–halide ion-pair components. A consistent ab initio computational study predicts the related energy barriers to alter significantly in the presence of the ion pair. Different channels are checked, with the carbon–halogen bond cleavage preceding or following the actual C-C bonding and with the counter-ions located closely or farther apart. The relative heights of the corresponding energy barriers are found to be switched by the ion pair. The above results suggest a possibility of facilitating such reactions without expensive catalysts.