Photolytic and Thermal Reactions of [C6H4(PPh2)2(μ-N2)] and Its Lewis Acid Adducts: N–N Bond Cleavage and Liberation of N2

The known species (Ph3P)2N2 was previously described as two phosphine donors associated with a doubly Lewis acidic N2-unit based on its thermal liberation of N2. Herein, we prepare the related species [C6H4(PPh2)2(μ-N2)] 4, where the cisoid chelation of the N2 fragment facilitates both N2 liberation and N-N bond cleavage reactions. In addition, these reactions can be achieved selectively via thermolysis of a Lewis acid adduct of 4 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 N2 capture and functionalization.