1997
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Abstract: A study of the redox behavior of the cobalt complex of octaethylbilindione (H3OEB), a biliverdin analog, reveals that coordination of the ligand allows its complexes to undergo reversible, one-electron transfer processes, whereas the free ligand itself undergoes an irreversible two-electron oxidation. Thus, the four-membered electron transfer series involving [Co(OEB)] n with n = +1, 0, −1, −2 has been observed electrochemically. The most highly oxidized member of this series has been isolated… Show more

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“…ground state could be expected even in the six‐coordinate case (see the 1 H NMR spectra in [D 6 ]DMSO, Figure 10). The FeI bond length of the triiodido complex 12 is about 0.09 Å longer than in the iodido derivative 9 , which suggests a very weak bond 32. The presence of a covalent bond, however, is clearly visible by the distortion of the easily polarizable I 3 − ligand.…”
Section: Resultsmentioning
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“…ground state could be expected even in the six‐coordinate case (see the 1 H NMR spectra in [D 6 ]DMSO, Figure 10). The FeI bond length of the triiodido complex 12 is about 0.09 Å longer than in the iodido derivative 9 , which suggests a very weak bond 32. The presence of a covalent bond, however, is clearly visible by the distortion of the easily polarizable I 3 − ligand.…”
Section: Resultsmentioning
“…The FeÀI bond length of the triiodido complex 12 is about 0.09 longer than in the iodido derivative 9, which suggests a very weak bond. [32] The presence of a covalent bond, however, is clearly visible by the distortion of the easily polarizable I 3 À ligand. The IÀIÀI angle of 174.45(2) 8 deviates slightly from linearity, and the IÀI bond lengths are quite unequal with 3.0834(5) and 2.7957(6) , suggesting a preformed split-off of an iodine molecule (bond length in crystalline I 2 : 2.68 [33] ).…”
Section: Axial Reactivitymentioning
“…(1). 9 Two members of this series, [Co(1b)] 3 and [Co(C 35 H 43 N 4 O 2 )] + 4 + , have been isolated and thoroughly characterized. The electronic structure of four-coordinate 3 has been described in terms of contributions from both the Co III / oeb 32 and Co II /oeb• 22 forms, where oeb• 22 is the radical obtained by one-electron oxidation of oeb 32 .…”
mentioning
“…Several porphyrinoids 14,15 and expanded porphyrin macrocycles [16][17][18][19] also stabilize unpaired π electrons. Besides macrocyclic structures, 20,21 early examples of linear oligopyrrolic radicals in metal complexes were found within the study of bilindiones (Chart 1, a), [22][23][24] but more recent reports highlighted the formation of stable ligand-based radicals in metal complexes of tetradentate bis(phenolate)-dipyrrins (Chart 1, b), [25][26][27][28][29] bis(2-aminophenyl)-dipyrrins, 30 and diimino-dipyrrins, 31 as well as tridentate tripyrrindione (Chart 1, c) 20,[32][33][34][35] and dihydrazonopyrrole 36,37 scaffolds.…”
Section: Introductionmentioning