Two cases of mediated electron transfer are presented: chloroform reduction catalysed by MoII/I alkoxy scorpionates and debromination of hexabromocyclododecane (HBCD) in the presence of free-base tetraphenylporphyrin (H2TPP). Although H2TPP should act as a typical outer-sphere mediator, it is not active towards analogous dehalogenation of 1,2-dibromocyclododecane. The observed phenomena can be rationalised by considering the catalytically relevant transient adducts formed owing to noncovalent interactions (Csingle bondH hydrogen bonds and dispersive Csingle bondhalogen⋯π interactions or directional halogen bonding), which warrants the close and prolonged contact between the catalyst and its substrate, thus increases the probability of electron transfer, and decisively accelerates the reaction. Crucial for this action is thermodynamic stability of the adducts, which can only be explained if dispersive van der Waals interactions are properly accounted for, e.g., as by dispersion-corrected density functional theory (DFT-D) calculations. The structures involving strong and anisotropic interactions, like the surprisingly short Csingle bondH⋯Oalkoxide H-bonding in the MoI–chloroform adduct, may be reasonably well described by standard DFT calculations and the energy needs only be corrected for dispersion without the need for structure re-optimisation at the DFT-D level. The latter is, however, a method of choice for the prediction of supramolecular structures chiefly controlled by weak non-directional van der Waals forces.