Chemistry of the Diazeniumdiolates I. Structural and Spectral Characteristics of the [N(O)NO]− Functional Group

• Published in: Nitric oxide Vol. 5; no. 4; pp. 377 - 394
• Main Authors: Keefer, Larry K., Flippen-Anderson, Judith L., George, Clifford, Shanklin, Anna P., Dunams, Tambra M., Christodoulou, Danae, Saavedra, Joseph E., Sagan, Elizabeth S., Bohle, D.Scott
• Format: Journal Article
• Language: English
• Published: United States Elsevier Inc 01-08-2001
• Subjects: Anions - chemistry; Chemical Phenomena; Chemistry, Physical; Crystallography, X-Ray; density functional theory calculations; infrared; Molecular Probe Techniques; nitric oxide; Nitric Oxide - chemistry; Nitric Oxide - metabolism; nitrogen-15; Spectrophotometry, Infrared; Spectrophotometry, Ultraviolet; Terminology as Topic; ultraviolet spectroscopy; X-ray crystallography; X-ray crystallography; nitric oxide; nitrogen-15; infrared; density functional theory calculations; ultraviolet spectroscopy
• ISSN: 1089-8603; 1089-8611
• DOI: 10.1006/niox.2001.0359

Ions of structure X[N(O)NO]−, examples of which have seen increasing use as probes for studying the biology of nitric oxide (NO) over the past decade, have a varied chemical history spanning nearly two centuries. Nevertheless, they have not been widely appreciated for their physicochemical similarities. Here we begin a series of systematic inquiries into the fundamental chemistry of such compounds aimed at identifying both the characteristics that justify considering them as a group and the factors that contribute to observed differences in their physicochemical properties. In the present paper, X-ray structures in which X is SO−3 (1), O− (2), Ph (3), and Et2N (5), as well as that of the gem-disubstituted carbon derivative CH2[N(O)NO]2−2 (4), are compared. All their O-N-N-O systems are essentially planar, with cis oxygens and an N-N linkage exhibiting considerable double-bond character. The ultraviolet spectrum of the isolated chromophore consists of a relatively intense (∼6–10 mM−1 cm−1 per [N(O)NO]− group) absorption at 248–250 nm (for 2 and 5) that is red shifted by through-space Stark interactions (e.g., by ∼10 nm in 1 and 4) as well as by conjugative interaction with X (λmax = 284 nm for 3). Infrared and Raman spectra for the widely used pharmacological probe 5 were determined, with analysis of vibrational modes being aided by comparison with the spectra of the [15N(O)15NO]− isotopomer and density functional theory calculations at the B3LYP/6-311++G** level. To address confusion that has arisen in the literature resulting from rather widespread use of differing trivial designations for this class of compounds, a unifying nomenclature system is recommended in which compounds containing the [N(O)NO]− moiety are named as diazeniumdiolates. It is hoped that these and other efforts to understand and predict the physicochemical similarities and differences among different members of the diazeniumdiolate class will aid in reaping their full potential in the area of rational drug design.