TY - JOUR
T1 - Oxidative nitration reaction of antiaromatic 5,15-dioxaporphyrin
AU - Nishiyama, Akihide
AU - Tanaka, Yuki
AU - Mori, Shigeki
AU - Furuta, Hiroyuki
AU - Shimizu, Soji
N1 - Funding Information:
This work was supported by Grants-in-Aids for Young Scientists (A), (JSPS KAKENHI Grant Number JP26708003), Scientific Research (B) (JSPS KAKENHI Grant Number JP19H02703), and Scientific Research on Innovative Area, “p-System Figuration: Control of Electron and Structural Dynamism for Innovative Functions (No. 2601)” (JSPS KAKENHI Grant Number JP17H05160).
PY - 2020/1/1
Y1 - 2020/1/1
N2 - Upon oxidation of 20π-electron antiaromatic 5,15-dioxaporphyrin (DOP) using nitrosonium ions as oxidants, a tetrakis-β-nitrated compound was formed instead of the expected 18π-electron aromatic dication species via an oxidative nitration reaction mechanism. Compared with the original DOP, this tetranitro DOP product exhibited a blue shift of absorption and downfield shifts of the β-pyrrolic proton signals. The unique antiaromatic electronic structure of the tetranitro DOP was disclosed experimentally by electrochemistry and theoretically by DFT and NICS calculations.
AB - Upon oxidation of 20π-electron antiaromatic 5,15-dioxaporphyrin (DOP) using nitrosonium ions as oxidants, a tetrakis-β-nitrated compound was formed instead of the expected 18π-electron aromatic dication species via an oxidative nitration reaction mechanism. Compared with the original DOP, this tetranitro DOP product exhibited a blue shift of absorption and downfield shifts of the β-pyrrolic proton signals. The unique antiaromatic electronic structure of the tetranitro DOP was disclosed experimentally by electrochemistry and theoretically by DFT and NICS calculations.
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U2 - 10.1142/S108842461950113X
DO - 10.1142/S108842461950113X
M3 - Article
AN - SCOPUS:85072527532
VL - 24
SP - 355
EP - 361
JO - Journal of Porphyrins and Phthalocyanines
JF - Journal of Porphyrins and Phthalocyanines
SN - 1088-4246
IS - 1-3
ER -