Photolytic and Thermal Reactions of [CH(PPh)(μ-N)] and Its Lewis Acid Adducts: N-N Bond Cleavage and Liberation of N.

The known species (PhP)N was previously described as two phosphine donors associated with a doubly Lewis acidic N-unit based on its thermal liberation of N. Herein, we prepare the related species [CH(PPh)(μ-N)] , where the chelation of the N fragment facilitates both N liberation and N-N bond cleavage reactions. In addition, these reactions can be achieved selectively via thermolysis of a Lewis acid adduct of or by direct photolysis, respectively. These findings provide insights on avenues to P(V) reduction, photochemical N-C bond formation, and the design of donor-acceptor combinations for N capture and functionalization.