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Regioselective Oxidative Ring Cleavage of Antiaromatic Nickel(II) Norcorrole to Dialkoxybis(dipyrrin)s
Author(s) -
Shafie Siham A.,
Kawashima Hiroyuki,
Miyake Yoshihiro,
Shinokubo Hiroshi
Publication year - 2019
Publication title -
chempluschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.801
H-Index - 61
ISSN - 2192-6506
DOI - 10.1002/cplu.201900068
Subject(s) - antiaromaticity , chemistry , regioselectivity , tautomer , cleavage (geology) , ring (chemistry) , enol , benzene , nickel , medicinal chemistry , solvent , photochemistry , oxidative cleavage , bond cleavage , stereochemistry , aromaticity , organic chemistry , molecule , catalysis , geotechnical engineering , fracture (geology) , engineering
The Ni(II) complex of meso ‐dimesitylnorcorrole is a stable 16π antiaromatic porphyrinoid. We have previously reported that the reaction of the norcorrole Ni(II) complex with m ‐chloroperbenzoic acid resulted in oxygen insertion to afford the corresponding 10‐ oxacorrole Ni(II) complex, which is an 18π aromatic porphyrinoid. In sharp contrast, we have found that treatment of the norcorrole Ni(II) complex with bis[(trifluoroacetoxy)iodo]benzene in the presence of a variety of alcohols induced a ring‐opening reaction to furnish the corresponding dialkoxybis(dipyrrin)s through regioselective oxidative C−C bond cleavage. Furthermore, dihydroxybis(dipyrrin) exhibited solvent‐dependent absorption and emission behavior through keto−enol tautomerization of the hydroxy groups.