Pavlos Christopher M, Cohen Andrew D, D'Sa Raechelle A, Sunoj R B, Wasylenko Walter A, Kapur Preeya, Relyea Heather A, Kumar Neema A, Hadad Christopher M, Toscano John P
Department of Chemistry, Johns Hopkins University, 3400 North Charles Street, Baltimore, MD 21218, USA.
J Am Chem Soc. 2003 Dec 3;125(48):14934-40. doi: 10.1021/ja034487y.
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 the formation 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 form triplet NO(-) and nitrosamine (minor process) or rapidly dissociates to form an additional molecule of NO and ultimately amine (major process). The production of nitrosamine radical anion 5 upon photolysis of diazeniumdiolate 3 is confirmed by low-temperature EPR spectroscopy. The calculated energetics for the ground and excited states of the parent diazeniumdiolate ion at the CIS and B3LYP levels of theory as well as B3LYP calculations on the fragmentation processes were very effective in rationalizing the observed photodissociation processes.
通过实验和计算方法研究了1-(N,N-二乙氨基)-重氮-1-鎓-1,2-二醇盐（3）钠盐的水相光化学。光解通过三重激发态导致N-亚硝基二乙胺自由基阴离子（5）和一氧化氮（NO）的形成。亚硝胺自由基阴离子要么在笼逃逸前与NO发生电子转移，形成三重态NO(-)和亚硝胺（次要过程），要么迅速解离，形成额外的NO分子并最终生成胺（主要过程）。通过低温EPR光谱证实了重氮二醇盐3光解时产生亚硝胺自由基阴离子5。在CIS和B3LYP理论水平上对母体重氮二醇盐离子的基态和激发态进行的能量计算，以及对碎片化过程的B3LYP计算，在合理解释观察到的光解离过程方面非常有效。
