1979
DOI: 10.1021/j100475a006
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One-electron reduction of aromatic nitrogen heterocycles in aqueous solution. 2,2'-Bipyridine and 1,10-phenanthroline

Abstract: Publication costs assisted by the National Science FoundationThe reaction of 2,2'-bipyridine (bpy), 1,lO-phenanthroline (phen), and their monoprotonated cations (bpyH+ and phenH+) with radiation-generated one-electron reducing agents yields radicals, the spectra, kinetics, and acid-base properties of which have been established. BpyH2+. has a pK, of 5.6 and exhibits an intense absorption maximum at 375 nm ( e 4.5 X lo4 M-l cm-' 1; bpyH. shows A, , , 365 nm ( E 3.0 X lo4 M-' cm-'). BpyH. decays via second-order… Show more

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Cited by 59 publications
(32 citation statements)
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References 15 publications
(21 reference statements)
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“…(5) implies the protonation of tmphen ÅÀ in the polymeric Re I complexes. Similar protonation processes have been observed in a variety of organic reactions involving radical anions [47], in the one-electron reduction of bpy and phen [48] by pulse radiolysis, in the electro-polymerization of Ru II poly-pyridinic complexes [49] and in pulse radiolysis reduction of several polymeric Re I complexes [1,10,37,50]. The process represented by Eq.…”
Section: Discussionsupporting
confidence: 59%
“…(5) implies the protonation of tmphen ÅÀ in the polymeric Re I complexes. Similar protonation processes have been observed in a variety of organic reactions involving radical anions [47], in the one-electron reduction of bpy and phen [48] by pulse radiolysis, in the electro-polymerization of Ru II poly-pyridinic complexes [49] and in pulse radiolysis reduction of several polymeric Re I complexes [1,10,37,50]. The process represented by Eq.…”
Section: Discussionsupporting
confidence: 59%
“…This observation supported by the absence of degenerate electron exchange at pH 13.3 can be accounted for by a reaction sequence that changes the structure of the radicals in the primary pair. The anion DP -• has pK a > 14, 49 thus the protonation reaction DP -• + H 2 O f DPH • + OH -occurs very fast with changing the spin density distribution in one of the partners in the primary radical pair. The changing of the electron spin density distribution and of the g-factor in radical G(-2H) -• as compared to G(-H) • occurs upon deprotonation and may lead to the changing of the CIDNP enhancement factors and of the rate of paramagnetic relaxation.…”
Section: Resultsmentioning
confidence: 99%
“…The free ligand tptz, similar to the complex Fe(tptz) 2 2+ , reacts with OH • or e aq − to form an adduct similar to terpy [9], bipy [6][7][8] and phen. Hence, the reaction may lead to an adduct, tptz(OH) • or Htptz(OH) •+ or H 2 tptz(OH) •2+ , depending on the pK a of tptz (2.19 and 3.40) [2].…”
Section: Resultsmentioning
confidence: 99%
“…OH • is a powerful oxidizing agent, while e aq − is a good reducing agent. OH • is known to react with metal complexes containing organic ligands forming an adduct in case of benzatopentammine cobalt(II) [5] and bipy [6][7][8].…”
Section: Introductionmentioning
confidence: 99%