Photochemistry of trans-Cr(cyclam)(ONO)2+, a Nitric Oxide Precursor
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- 作者：Alexis D. Ostrowski ; Ryan O. Absalonson ; Malcolm A. De Leo ; Guang Wu ; James G. Pavlovich ; Janet Adamson ; Bilal Azhar ; Alexei V. Iretskii ; Ian L. Megson ; Peter C. Ford
- 刊名：Inorganic Chemistry
- 出版年：2011
- 出版时间：May 16, 2011
- 年：2011
- 卷：50
- 期：10
- 页码：4453-4462
- 全文大小：1017K
- 年卷期：v.50,no.10(May 16, 2011)
- ISSN：1520-510X
文摘
Experimental and density functional theory (DFT) studies are described that are focused on outlining the reactivity of the known photochemical nitric oxide precursor trans-Cr(cyclam)(ONO)2+ (鈥淐rONO鈥? cyclam = 1,4,8,11-tetrazacycltetradecane). Studies in both aerated and deaerated aqueous media are described as are the roles of both the oxidant O2 and a reductant such as glutathione in trapping the apparent Cr(IV) photoreaction intermediate trans-Cr(cyclam)(O)(ONO)+. Also reported and characterized structurally is the Cr(V) product of long-term photolysis in the absence of reducing agents, the trans-dioxo species [trans-Cr(cyclam)(O)2](ClO4). Photosensitization experiments indicate that at least a significant fraction of the reaction occurs from the lowest energy doublet excited state(s). Lastly, cell culture experiments demonstrate that CrONO has little or no acute toxicity either before or after photolysis.