Nitrogen-15 magnetic resonance spectroscopy of trioxodinitrate: N-protonation of an oxoanion

Bonner, Francis T.; Degani, Hadassa; Akhtar, M. Humayoun

doi:10.1021/ja00403a021

Cited by 23 publications

(20 citation statements)

References 2 publications

(3 reference statements)

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“…Initial protonation occurs at the nitroso group oxygen followed by a rate-limiting tautomerization to give a monoanion protonated at the nitroso nitrogen atom, a structure supported by 15 N NMR and Raman spectroscopy ( Fig. 5) (10). Heterolytic cleavage of the N-N bond yields the observed products HNO and nitrite (Fig.…”

Section: Structure/synthesismentioning

confidence: 76%

The Chemistry of Nitroxyl-Releasing Compounds

DuMond

King

2011

Antioxidants & Redox Signaling

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Nitroxyl (HNO) demonstrates a diverse and unique biological profile compared to nitric oxide, a redox-related compound. Although numerous studies support the use of HNO as a therapeutic agent, the inherent chemical reactivity of HNO requires the use of donor molecules. Two general chemical strategies currently exist for HNO generation from nitrogen-containing molecules: (i) the disproportionation of hydroxylamine derivatives containing good leaving groups attached to the nitrogen atom and (ii) the decomposition of nitroso compounds (X-N=O, where X represents a good leaving group). This review summarizes the synthesis and structure, the HNO-releasing mechanisms, kinetics and by-product formation, and alternative reactions of six major groups of HNO donors: Angeli's salt, Piloty's acid and its derivatives, cyanamide, diazenium diolate-derived compounds, acyl nitroso compounds, and acyloxy nitroso compounds. A large body of work exists defining these six groups of HNO donors and the overall chemistry of each donor requires consideration in light of its ability to produce HNO. The increasing interest in HNO biology and the potential of HNO-based therapeutics presents exciting opportunities to further develop HNO donors as both research tools and potential treatments.

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Section: Structure/synthesismentioning

confidence: 76%

The Chemistry of Nitroxyl-Releasing Compounds

DuMond

King

2011

Antioxidants & Redox Signaling

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“…However, the free acid has been suggested to in fact have a substantially higher stability than the monoanion [4] due to conversion from Nto O-protonation [67]. The stability toward decomposition of the most thermodynamically stable diprotonated species was corroborated recently by quantum mechanical calculation [8].…”

Section: Angeli's Salt and Piloty's Acidmentioning

confidence: 97%

“…The decomposition of Angeli's salt is reversible, as demonstrated by modest inhibition of the rate in the presence of excess nitrite [6,65]. Interestingly, only the monobasic species protonated at the nitroso nitrogen was observable by Raman and 15 N NMR spectroscopy [66,67]. The position of the second proton in the free acid has not been determined spectroscopically.…”

Section: Angeli's Salt and Piloty's Acidmentioning

confidence: 99%

Donors of HNO

Miranda

Nagasawa

Toscano

2005

CTMC

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Recent comparisons of the pharmacological effects of nitric oxide (NO) and nitroxyl (HNO) donors have demonstrated that the responses to these redox-related nitrogen oxides are nearly universally dissimilar. These analyses have suggested the existence of mutually exclusive signaling pathways as a result of discrete chemical interactions of HNO and NO with a variety of critical biomolecules. Although the mechanisms of action are currently unresolved, the pharmacological responses to HNO are promising for clinical treatment of cardiovascular diseases such as heart failure, myocardial infarction and stroke. This review provides a detailed discussion of the most commonly utilized donors of HNO as well as a guideline for the characterization of novel donors.

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“…(iv) Recent "N NMR studies [40] on oxyhyponitrite have shown that the most basic site (pK, = 9.7) is the nitrogen atom shown as coordinated to iron in V. Although there is no strict correlation between basicity and tendency to form metal complexes, this observation together with the known affinity of Fe(H) for unsaturated nitrogenous ligands (rather than oxygen) suggests that complex V is not unreasonable. In short, all of the intermediate steps involve known chemical species, and each reaction has sound chemical precedent.…”

Section: Introductionmentioning

confidence: 98%