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In fact, UV-vis & EPR spectroscopy, along with ESI-MS interrogation indicates low-temperature formation of solutions with Cu(II) plus a phenoxyl radical (thus oxygenation has already occurred) when reaction solutions are left at -44°C.13 No evidence was obtained which could relate to the identification of any new species, for example, a cupryl species
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13 No evidence was obtained which could relate to the identification of any new species, for example, a cupryl species.
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We note that in similarly constructed CuII--OOH complexes with modified TMPA frameworks, Masuda14,18 has shown that a 6-N-H group on pyridyl-ligand arms hydrogen-bonds to the proximal oxygen atom of a CuII-hydroperoxo group. Thus, the ortho C-H substrate of the 6-aryl moiety of 6tBP may certainly be in close proximity to either a hydroperoxo O-atom of, 6tbpCuII(-OOH, 2) or oxo atom of a high-valent Cu-O intermediate
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-OOH)]+ (2) or oxo atom of a high-valent Cu-O intermediate.
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20 recently describe the Cu-(II)-promoted aryl hydroxyiation of a 2-phenylpyridyl moiety, suggesting the reaction proceeds via electron-transfer giving an aryl cation-radical, nucleophilic ring attack, etc.
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20 recently describe the Cu-(II)-promoted aryl hydroxyiation of a 2-phenylpyridyl moiety, suggesting the reaction proceeds via electron-transfer giving an aryl cation-radical, nucleophilic ring attack, etc.
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2TPA = (2-pyridylmethyl)bis(6-methyl-2-pyridylmethyl) amine.
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2TPA = (2-pyridylmethyl)bis(6-methyl-2-pyridylmethyl) amine.
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