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Diels–Alder Reaction on Free C 68 Fullerene and Endohedral Sc 3 N@C 68 Fullerene Violating the Isolated Pentagon Rule: Importance of Pentagon Adjacency
Author(s) -
Yang Tao,
Zhao Xiang,
Nagase Shigeru,
Akasaka Takeshi
Publication year - 2014
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201402435
Subject(s) - pentagon , cycloaddition , fullerene , reactivity (psychology) , chemistry , regioselectivity , adjacency list , cluster (spacecraft) , computational chemistry , density functional theory , crystallography , photochemistry , organic chemistry , catalysis , combinatorics , medicine , alternative medicine , mathematics , pathology , computer science , programming language , political science , law
The reaction mechanism and regioselectivity of the Diels–Alder reactions of C 68 and Sc 3 N@C 68 , which violate the isolated pentagon rule, were studied with density functional theory calculations. For C 68 , the [5,5] bond is the most favored thermodynamically, whereas the cycloaddition on the [5,6] bond has the lowest activation energy. Upon encapsulation of the metallic cluster, the exohedral reactivity of Sc 3 N@C 68 is reduced remarkably owing to charge transfer from the cluster to the fullerene cage. The [5,5] bond becomes the most reactive site thermodynamically and kinetically. The bonds around the pentagon adjacency show the highest chemical reactivity, which demonstrates the importance of pentagon adjacency. Furthermore, the viability of Diels–Alder cycloadditions of several dienes and Sc 3 N@C 68 was examined theoretically. o ‐Quinodimethane is predicted to react with Sc 3 N@C 68 easily, which implies the possibility of using Diels–Alder cycloaddition to functionalize Sc 3 N@C 68 .