Photochemistry of 1-(N,N-Diethylamino)diazen-1-ium-1,2-diolate: An Experimental and Computational Investigation
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- 作者：Christopher M. Pavlos ; Andrew D. Cohen ; Raechelle A. D'Sa ; R. B. Sunoj ; Walter A. Wasylenko ; Preeya Kapur ; Heather A. Relyea ; Neema A. Kumar ; Christopher M. Hadad ; and John P. Toscano
- 刊名：Journal of the American Chemical Society
- 出版年：2003
- 出版时间：December 3, 2003
- 年：2003
- 卷：125
- 期：48
- 页码：14934 - 14940
- 全文大小：120K
- 年卷期：v.125,no.48(December 3, 2003)
- ISSN：1520-5126
文摘
The aqueous photochemistry of the sodium salt of 1-(N,N-diethylamino)-diazen-1-ium-1,2-diolate(3) has been investigated by both experimental and computational methods. Photolysis results in theformation of the N-nitrosodiethylamine radical anion (5) and nitric oxide (NO) via a triplet excited state.The nitrosamine radical anion either undergoes electron transfer with NO before cage escape to formtriplet NO- and nitrosamine (minor process) or rapidly dissociates to form an additional molecule of NOand ultimately amine (major process). The production of nitrosamine radical anion 5 upon photolysis ofdiazeniumdiolate 3 is confirmed by low-temperature EPR spectroscopy. The calculated energetics for theground and excited states of the parent diazeniumdiolate ion at the CIS and B3LYP levels of theory aswell as B3LYP calculations on the fragmentation processes were very effective in rationalizing the observedphotodissociation processes.