Electron spin resonance study of iminyl and triazenyl radicals derived from organic azides

Cooper, J.; Roberts, Brian P.; Winter, Jeremy N.

doi:10.1039/c39770000320

Cited by 24 publications

(14 citation statements)

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“…[13] Using the Cym/CH 3 CN co-ligand combination with a less-basic but p-accepting arene in 3 2+ , the spin density on ruthenium diminishes further (g 1 Àg 3 < 0.02), and a hyperfine structure becomes resolved, typical for radical species (Figure 2 b). [14] The EPR results (Table 1), demonstrating the triazenyl radical ligand character in 3 2+ (Figure 2 b) and, to a lesser extent, in 2 2+ are supported by DFT calculations (Table 2). [14] The EPR results (Table 1), demonstrating the triazenyl radical ligand character in 3 2+ (Figure 2 b) and, to a lesser extent, in 2 2+ are supported by DFT calculations (Table 2).…”

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confidence: 60%

Discovering More Non‐Innocence: Triazenido versus Triazenyl Radical Ligand Function, and a Comment on [NO₂]ⁿ as a “Suspect” Ligand

et al. 2013

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confidence: 60%

Discovering More Non‐Innocence: Triazenido versus Triazenyl Radical Ligand Function, and a Comment on [NO₂]ⁿ as a “Suspect” Ligand

et al. 2013

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“…Radicals 2-33 correspond to N-centered radicals: alkylaminyl radicals (2-8); radical cations of acyclic alkylamines (9)(10)(11)(12)(13)(14)(15)(16)(17)(18); radical cations of cyclic alkylamines (19)(20)(21)(22)(23)(24)(25)(26); iminyl radicals (27)(28)(29)(30)(31); azaphenyl radicals (32 and 33). Radicals 34-63 correspond to NN-centered radicals: alkylhydrazyl radicals (34)(35)(36)(37)(38)(39); radical cations of alkylhydrazines (40)(41)(42)(43)(44)(45)(46)(47)(48)(49)(50)(51)(52)(53); radical cations of alkyldiamines (54)(55)(56)(57); radical ions of alkylazoalkanes (58-63). Radicals 64-106 correspond to NOand NO 2 -centered radicals: alkylnitroxyl radicals (64-79); radical anions of nitroalkanes (80)…”

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confidence: 99%

Density Functional Theory Study of ¹⁴N Isotropic Hyperfine Coupling Constants of Organic Radicals

et al. 2006

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Nitrogen hyperfine coupling constants (hfccs) of organic radicals have been calculated by density functional theory (DFT) methodology. The capability of the B3LYP functional, combined with 6-31G*, TZVP and EPR-III basis sets, to reproduce experimental nitrogen coupling constant data has been analyzed for 109 neutral, cationic and anionic radicals, all of them containing at least one nitrogen atom. The results indicate that the selection of the basis set plays an important role in the accuracy of DFT calculations of hfccs, mainly in relation with the composition of the primitive functions and the quantum number of those functions. The main conclusion obtained is the high reliability of the scheme B3LYP/6-31G* for the prediction of nitrogen hfccs with very low computational cost.

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“…In 1977 Cooper et al (15) reported that photochemically generated tert-butoxy radicals reacted with alkyl azides to produce iminyl radicals 'cleanly' and at concentrations suitable for epr spectroscopic study. This procedure worked well with cyclopentyl azide and, over the temperature range (-10 to 40°C, vide infra), the epr spectrum of the cyclopentylketiminyl was entirely free of the 4-cyanobutyl spectrum.…”

Section: Introductionmentioning

confidence: 99%

Cyclization of the 4-cyanobutyl radical

Griller¹,

Schmid²,

Ingold³

1979

Can. J. Chem.

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. INGOLD. Can. J. Chem. 57,831 (1979). The rate constant for the irreversible cyclization of the 4-cyanobutyl radical to the cyclopentiminyl radical, kcCzN, has been measured from -52 to 12°C by kinetic epr spectroscopy. The temperature dependence of this rate constant can be represented by, log (k,C'N/s-') = (9.9 2 1.0) -(8.6 t l.0)/8 where 8 = 2.3RT kcal/mol. This rearrangement is somewhat slower than the analogous cyclizations of the 5-hexenyl and 5-hexynyl radicals.DAVID GRILLER, PETER SCHMID et KEITH U. INGOLD. Can. J. Chem. 57,831 (1979). On a mesurk les constantes de vitesse de la cyclisation irrtversible du radical cyano-4 butyle en radical cyclopentiminyle, kcCEN, a des tempkratures allant de -52 a 12°C en faisant appel a la spectroscopie rpe. On peut reprtsenter la relation entre la constante de vitesse et la temptrature grlce a l'tquation oh 0 = 2.3RT kcal/mol. Cette transposition est un peu plus lente que les cyclisations analogues des radicaux hexenyle-5 et hexynyle-5.[Traduit par le journal]

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Electron spin resonance study of iminyl and triazenyl radicals derived from organic azides

Cited by 24 publications

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Discovering More Non‐Innocence: Triazenido versus Triazenyl Radical Ligand Function, and a Comment on [NO₂]ⁿ as a “Suspect” Ligand

Discovering More Non‐Innocence: Triazenido versus Triazenyl Radical Ligand Function, and a Comment on [NO₂]ⁿ as a “Suspect” Ligand

Density Functional Theory Study of ¹⁴N Isotropic Hyperfine Coupling Constants of Organic Radicals

Cyclization of the 4-cyanobutyl radical

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Electron spin resonance study of iminyl and triazenyl radicals derived from organic azides

Cited by 24 publications

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Discovering More Non‐Innocence: Triazenido versus Triazenyl Radical Ligand Function, and a Comment on [NO2]n as a “Suspect” Ligand

Discovering More Non‐Innocence: Triazenido versus Triazenyl Radical Ligand Function, and a Comment on [NO2]n as a “Suspect” Ligand

Density Functional Theory Study of 14N Isotropic Hyperfine Coupling Constants of Organic Radicals

Cyclization of the 4-cyanobutyl radical

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Discovering More Non‐Innocence: Triazenido versus Triazenyl Radical Ligand Function, and a Comment on [NO₂]ⁿ as a “Suspect” Ligand

Discovering More Non‐Innocence: Triazenido versus Triazenyl Radical Ligand Function, and a Comment on [NO₂]ⁿ as a “Suspect” Ligand

Density Functional Theory Study of ¹⁴N Isotropic Hyperfine Coupling Constants of Organic Radicals