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Keywords:

  • acidity function;
  • disproportionation;
  • kinetics;
  • nitroxyl radicals;
  • reduction potentials

Acid-catalyzed disproportionation of cyclic nitroxyl radicals R2NO includes the half-reactions of their oxidation to oxoammonium cations R2NO+ and reduction to hydroxylamines R2NOH. For many nitroxyl radicals, this reaction is characterized by its ~100% reversibility. Quantitative characteristics of acid–base and redox properties of the whole redox triad may be obtained from research of kinetics and equilibrium of this reaction. Here, we have examined the kinetics for the disproportionation of twenty piperidine-, pyrroline-, pyrrolidine-, and imidazoline nitroxyl radicals in aqueous H2SO4, and interpreted it in terms of the excess acidity function X. The rate-limiting step of this reaction is R2NO oxidation by its protonated counterpart R2NOH+•. Kinetic stability of R2NO in acidic media depends on the basicity of nitroxyl group. This basicity is influenced predominantly by protonation of another, more basic group in radical structure, and its proximity to nitroxyl group. The discovered estimates of pK values for radical cations R2NOH+• (from −5.8 to −12.0) indicate a very low basicity of nitroxyl groups in all commonly used R2NO. For the first time, a linear correlation is obtained between the one-electron reduction potentials of oxoammonium cations and the basicity of nitroxyl groups of related radicals. Copyright © 2013 John Wiley & Sons, Ltd.

Featured Compounds

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  1. 1 - 29
Compound 2
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 1
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 3
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 1a
Molecular Weight:156.2453
Molecular Formula:C9H18NO
InChIKey:VUZNLSBZRVZGIK-UHFFFAOYSA-N
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Compound 1c
Molecular Weight:172.2447
Molecular Formula:C9H18NO2
InChIKey:CSGAUKGQUCHWDP-UHFFFAOYSA-N
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Compound 1d
Molecular Weight:190.69
Molecular Formula:C9H17ClNO
InChIKey:URDZAZJWDUZUSJ-UHFFFAOYSA-N
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Compound 1f
Molecular Weight:213.2966
Molecular Formula:C11H21N2O2
InChIKey:YYTYIUAYFBFKHX-UHFFFAOYSA-N
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Compound 1g
Molecular Weight:275.366
Molecular Formula:C16H23N2O2
InChIKey:CLVYZUDDADZKSG-UHFFFAOYSA-N
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Compound 1i
Molecular Weight:276.3508
Molecular Formula:C16H22NO3
InChIKey:DRFYZAIGLPMIOS-UHFFFAOYSA-N
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Compound 1j
Molecular Weight:200.2548
Molecular Formula:C10H18NO3
InChIKey:GVQKWFQBWZOJHV-UHFFFAOYSA-N
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Compound 1o
Molecular Weight:170.2288
Molecular Formula:C9H16NO2
InChIKey:KMEUSKGEUADGET-UHFFFAOYSA-N
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Compound 1p
Molecular Weight:183.2276
Molecular Formula:C9H15N2O2
InChIKey:GMXOTWPDUBXCMS-UHFFFAOYSA-N
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Compound 1q
Molecular Weight:184.2124
Molecular Formula:C9H14NO3
InChIKey:SADYUZSTFFUBBP-UHFFFAOYSA-N
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Compound 1r
Molecular Weight:172.2447
Molecular Formula:C9H18NO2
InChIKey:NVSLLEANKLJTSO-UHFFFAOYSA-N
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Compound 1b
Molecular Weight:186.2713
Molecular Formula:C10H20NO2
InChIKey:KRNWYBIEWUXCOB-UHFFFAOYSA-N
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Compound 1e
Molecular Weight:213.2966
Molecular Formula:C11H21N2O2
InChIKey:YNLLOYGIUCKETH-UHFFFAOYSA-N
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Compound 1k
Molecular Weight:171.26
Molecular Formula:C9H19N2O
InChIKey:AYSOUYKQIUYGFR-UHFFFAOYSA-N
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Compound 1m
Molecular Weight:230.3254
Molecular Formula:C15H20NO
InChIKey:PALUVXQWTWKGOX-UHFFFAOYSA-N
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Compound 1s
Molecular Weight:185.2435
Molecular Formula:C9H17N2O2
InChIKey:UXDLYVBMRUIQCX-UHFFFAOYSA-N
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Compound 1h
Molecular Weight:242.3379
Molecular Formula:C12H24N3O2
InChIKey:YNQJGNRWCBGNIP-UHFFFAOYSA-N
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Compound 1l
Molecular Weight:214.3476
Molecular Formula:C12H26N2O
InChIKey:IVGMTLVJDBDFDE-UHFFFAOYSA-N
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Compound 1n
Molecular Weight:212.2655
Molecular Formula:C11H18NO3
InChIKey:NBUBWSNMXCKHRP-UHFFFAOYSA-N
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Compound 1t
Molecular Weight:186.2282
Molecular Formula:C9H16NO3
InChIKey:CLKPVQZFNYXFCY-UHFFFAOYSA-N
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Compound 1u
Molecular Weight:233.2863
Molecular Formula:C13H17N2O2
InChIKey:MLSJXLQAJPYPSI-UHFFFAOYSA-N
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Compound 1H+
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 3H+
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 4u
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 2u
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 3u
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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