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Reactions of C 60 with Pyridazine and Phthalazine
Author(s) -
Hashikawa Yoshifumi,
Li Hui,
Murata Yasujiro
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202100711
Subject(s) - phthalazine , pyridazine , chemistry , computational chemistry , photochemistry , stereochemistry , medicinal chemistry
Cage‐opened bisfulleroids are one of suitable building blocks for making a large hole on fullerenes. This work focuses on the Diels‐Alder reaction of C 60 with azines, among synthetic methods developed thus far, to provide bisfulleroids. Surprisingly, the computational study predicted that the reaction proceeds with normal electron demand in contrast to hitherto considered inverse‐electron‐demand pathway. The benzoannulation to the pyridazine ring, i. e., phthalazine, resulted in the remarkably shortened reaction time due to the better interaction between the HOMO of phthalazine and the LUMO of C 60 as well as stronger 2,3‐diaza‐1,3‐butadiene character in the phthalazine as confirmed crystallographically. Contrary to expectations, the benzobisfulleroid was converted into corresponding orifice‐enlarged derivative via the photooxygenation slightly faster than the fulleroid derived from pyridazine.