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

Abstract

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.