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In‐Depth Understanding of the Chemical Properties of Rarely Explored Carbide Cluster Metallofullerenes: A Case Study of Sc 2 C 2 @ C 3 v (8)‐C 82 that Reveals a General Rule
Author(s) -
Cai Wenting,
Chen Muqing,
Bao Lipiao,
Xie Yunpeng,
Akasaka Takeshi,
Lu Xing
Publication year - 2015
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.201405493
Subject(s) - chemistry , cluster (spacecraft) , crystallography , scandium , fullerene , carbide , reactivity (psychology) , derivative (finance) , crystal structure , stereochemistry , inorganic chemistry , organic chemistry , medicine , alternative medicine , pathology , computer science , financial economics , economics , programming language
The chemical properties of carbide‐cluster metallofullerenes (CCMFs) remain largely unexplored, although several new members of CCMFs have been discovered recently. Herein, we report the reaction between Sc 2 C 2 @ C 3 v (8)‐C 82 , which is viewed as a prototypical CCMF because of its high abundance, and 3‐triphenylmethyl‐5‐oxazolidinone ( 1 ) to afford the corresponding pyrrolidino derivative Sc 2 C 2 @ C 3 v (8)‐C 82 (CH 2 ) 2 NTrt ( 2 ; Trt=triphenylmethyl). Single‐crystal X‐ray crystallography studies of 2 revealed that the reaction takes place at a [6,6]‐bond junction, which is directly over the encapsulated C 2 unit and is far from either of the two scandium atoms. On the basis of theoretical calculations and by considering previously reports, we have found that a hexagonal carbon ring on the cage of Sc 2 C 2 @ C 3 v (8)‐C 82 is highly reactive toward different reagents due to the overlap of high p‐orbital axis vector (POAV) angles and large LUMO coefficients. We propose that this highly concentrated area of reactivity is generated by the encapsulation of the Sc 2 C 2 cluster because this region is absent from the empty fullerene C 3 v (8)‐C 82 . Moreover, the absorption and electrochemical results confirm that derivative 2 is more stable than pristine Sc 2 C 2 @ C 3 v (8)‐C 82 , thus illuminating its potential applications.