Reaction of MBr₂ with 3 equiv of [K(18-crown-6)][O₂N₂CPh₃] generates the trityl diazeniumdiolate complexes [K(18-crown-6)][M(O₂N₂CPh₃)₃] (M = Co, 2; Fe, 3) in good yields. Irradiation of 2 and 3 using 371 nm light led to NO formation in 10 and 1% yields (calculated assuming a maximum of 6 equiv of NO produced per complex), respectively. N₂O was also formed during the photolysis of 2, in 63% yield, whereas photolysis of 3 led to the formation of N₂O, as well as Ph₃CN(H)OCPh₃, in 37 and 5% yields, respectively. These products are indicative of diazeniumdiolate fragmentation via both C-N and N-N bond cleavage pathways. In contrast, oxidation of complexes 2 and 3 with 1.2 equiv of [Ag(MeCN)₄][PF₆] led to N₂O formation but no NO formation, suggesting that diazeniumdiolate fragmentation occurs exclusively via C-N bond cleavage under these conditions. While the photolytic yields of NO are modest, they represent a 10- to 100-fold increase compared to the previously reported Zn congener, suggesting that the presence of a redox-active metal center favors NO formation upon trityl diazeniumdiolate fragmentation.

Exposure of [K(18-crown-6)(THF)₂][CPh₃] (THF = tetrahydrofuran; Ph = phenyl) to an atmosphere of nitric oxide (NO) cleanly generates [K(18-crown-6)][O₂N₂CPh₃] (1) in excellent yields. A subsequent reaction of [ZnCl₂(THF)₂] with 3 equiv of 1 affords the C-diazeniumdiolate complex [K(18-crown-6)][Zn(O₂N₂CPh₃)₃] (2). Both 1 and 2 were characterized by ¹H and ¹³C{¹H} NMR spectroscopy, and their structures were confirmed by X-ray crystallography. Photolysis of 2 using 371 nm light resulted in the formation of three trityl-containing products, namely, Ph₃CH, 9-phenylfluorene, and Ph₃CN(H)OCPh₃ (3). In addition, we detected nitrous oxide (N₂O), as well as small amounts of NO in the reaction mixture. In contrast, oxidation of 2 with 1.2 equiv of [Ag(MeCN)₄][PF₆] resulted in the formation of O(CPh₃)₂ as the major trityl-containing product; N₂O was also detected in the reaction mixture, but NO was not apparently formed in this case. The observation of these fragmentation products indicates that the [O₂N₂CPh₃]^- ligand is susceptible to both C-N bond and N-N bond cleavage. Moreover, the different product distributions suggest that [O₂N₂CPh₃]^- is susceptible to different modes of fragmentation.