Biphenalenylidene: Isolation and Characterization of the Reactive Intermediate on the Decomposition Pathway of Phenalenyl Radical

• Published in: Journal of the American Chemical Society Vol. 138; no. 7; pp. 2399 - 2410
• Main Authors: Uchida, Kazuyuki, Ito, Soichi, Nakano, Masayoshi, Abe, Manabu, Kubo, Takashi
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 24.02.2016; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; SIGMA-BOND; GROUND-STATE; SPECTROSCOPY; PLEIADENE; SUBSTITUENTS; CHEMISTRY; OPEN-SHELL; SOLID-STATE; HYDROCARBON; DIMERIZATIONS
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.5b13033

First isolation and characterization of biphenalenylidenes, which have long been unidentified reactive intermediates on the decomposition pathway of phenalenyl radical, were accomplished. Photoinduced electrocyclic ring-opening reaction of anti-dihydroperopyrene resulted in a successful conversion to E-biphenalenylidene, which enabled a detailed investigation of the electronic structure of E-biphenalenylidene by means of spectroscopic techniques. A stereoisomer, Z-biphenalenylidene, was also observed by suppressing a facile E–Z isomerization to E-biphenalenylidene in a rigid matrix. Furthermore, Z-biphenalenylidene demonstrated a thermal ring-closure in conrotatory process, which is not conforming to the Woodward–Hoffmann rule. These unusual reactivities of biphenalenylidene are ascribed to the ground states destabilized by its singlet biradical character, which was fully supported by theoretical calculations. The presence of E-biphenalenylidene on the decomposition pathway of phenalenyl was confirmed experimentally, leading to the full understanding of the decomposition mechanism of phenalenyl.