Radical reactivity of antiaromatic Ni(II) norcorroles with azo radical initiators
Siham Asyiqin Shafie1, Ryo Nozawa1, Hideaki Takano1,2
1Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering and Integrated Research Consortium Chemical Sciences (IRCCS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, Japan.
Abstract:
Norcorrole is a stable 16π-antiaromatic porphyrinoid that exhibits characteristic reactivities and physical properties. Here, we disclose the reaction of Ni(II) norcorroles with alkyl radicals derived from azo radical initiators. The radical selectively attacked the distal α-position relative to the meso-position to construct a nonaromatic bowl-shaped structure. The photophysical and electrochemical properties of the obtained radical adducts were compared to those of the parent Ni(II) norcorrole. The radical reactivity of Ni(II) norcorroles was investigated by density functional theory (DFT) calculations.
More Related Videos
09:35Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
07:12Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
Related Concept Videos
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
Radical Reactivity: Nucleophilic Radicals
Aryldiazonium Salts to Azo Dyes: Diazo Coupling
Radical Reactivity: Overview
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
