Details

Autor(en) / Beteiligte

• Baeza Cinco, Miguel Á.
• Kräh, Sabrina
• Guzman, Camilo F.
• Wu, Guang
• Hayton, Trevor W.

Titel

Photolytic or Oxidative Fragmentation of Trityl Diazeniumdiolate (O2N2CPh3 –): Evidence for Both C–N and N–N Bond Cleavage

Ist Teil von

• Inorganic chemistry, 2022-09, Vol.61 (38), p.14924-14928

Ort / Verlag

American Chemical Society

Erscheinungsjahr

2022

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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.