1980
DOI: 10.1021/j100454a011
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Nucleophilic addition of .alpha.-hydroxyalkyl radicals to polypyridyl complexes of chromium(III), cobalt(III), rhodium(III), and ruthenium(II) in aqueous solution

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Cited by 27 publications
(10 citation statements)
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“…The dose-corrected absorbance changes from the pulse-radiolysis experiments in N 2 O-saturated EtOH/H 2 O agree well with the difference spectrum in acetonitrile, indicating the formation of the ligand-centered radical Ru(menbpy) 3 •+ (Figure ). Although the CH 3 C • HOH radical does not reduce Ru(bpy) 3 2+ at pH 7 ( E ° ≈ −1.3 V vs NHE), the reduction potential of Ru(menbpy) 3 2+/+ is significantly more positive, −0.90 V vs NHE in water. CH 3 C • HOH (−1.25 V at pH 7) reduces Ru(menbpy) 3 2+ with a rateconstant of (8.2 ± 0.5) × 10 8 M -1 s -1 .…”
Section: Resultsmentioning
confidence: 94%
“…The dose-corrected absorbance changes from the pulse-radiolysis experiments in N 2 O-saturated EtOH/H 2 O agree well with the difference spectrum in acetonitrile, indicating the formation of the ligand-centered radical Ru(menbpy) 3 •+ (Figure ). Although the CH 3 C • HOH radical does not reduce Ru(bpy) 3 2+ at pH 7 ( E ° ≈ −1.3 V vs NHE), the reduction potential of Ru(menbpy) 3 2+/+ is significantly more positive, −0.90 V vs NHE in water. CH 3 C • HOH (−1.25 V at pH 7) reduces Ru(menbpy) 3 2+ with a rateconstant of (8.2 ± 0.5) × 10 8 M -1 s -1 .…”
Section: Resultsmentioning
confidence: 94%
“…The rate constant for this reaction is 7.5 ¥ 10 10 dm 3 mol -1 s -1 . 30 The spectra in Fig. 10 may be compared with the spectra obtained in spectroelectrochemical experiments (Fig.…”
Section: Reaction Of E -mentioning
confidence: 99%
“…It has been observed that adduct formation with cobalt(II1)-amine complexes and alcohol radicals is possible. 29 We suggest that adduct formation of the isopropyl radical with the p-superoxo complex leads to the formation of an isomer of the peroxo complex 0 I \! /O\-' I / / \ /"r\ "i instead of the isomer which has lower molar absorptivity.15 Alternatively, part of the reduction proceeds through the cobalt(II1) center which leads to the intramolecular isomer formation as shown 0 I Isopropyl radical reduces p-p-nitrobenzoato-di-phydroxo-bis(tetraminecobalt(II1)) with a rate constant of 2 X lo9 M-' s-l, and it is shown in that study that the reduction occurs initially at the bridging aromatic ring.22 Later on, the reduced ligand transfers the electron at a slower rate to reduce the cobalt(II1) center.…”
mentioning
confidence: 95%
“…The redox behavior of the 2-propanol radical with polypyridyl transition metal complexes also shows behavior different from the C H 2 0 H and CH,CHOH radicals. 29 It was suggested that the radical forms an adduct with the ligands in an initial step before reduction takes place. It has been observed that adduct formation with cobalt(II1)-amine complexes and alcohol radicals is possible.…”
mentioning
confidence: 99%