Characterization of a Lewis adduct in its inner and outer forms

The entrance channel of bimolecular reactions sometimes involves the formation of outer complexes as weakly bound, fleeting intermediates. Here, we characterize such an outer complex in a system that models the bimolecular, C-O bond-forming reaction of a phosphine oxide Lewis base with a carbenium Lewis acid. Crystallographic studies show that the C-O distance in the outer form exceeds that of the final or inner adduct by 1.1 angstroms. As the system samples the two forms of the complex, which correspond to minima on the corresponding potential energy surface, the C-O linkage switches from a secondary interaction in the outer complex to a dative bond in the inner complex. This phenomenon is harnessed as a functional feature to stabilize xanthylium-based photoredox catalysts.