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• W2334335068 startingPage "3139" @default.
• W2334335068 abstract "Little is known about the chemical properties of carbide cluster metallofullerenes (CCMFs). Here we report the photochemical reaction of a newly assigned CCMF Sc(2)C(2)@C(2v)(5)-C(80) with 2-adamantane-2,3-[3H]-diazirine (AdN(2), 1), which provides a carbene reagent under irradiation. Five monoadduct isomers (2a-2e), with respective abundances of 20%, 40%, 25%, 5%, and 10%, were isolated and characterized with a combination of experimental techniques including unambiguous single-crystal X-ray crystallography. Results show that the two Sc atoms of the bent Sc(2)C(2) cluster tend to move in most cases, whereas the C(2)-unit is almost fixed. Accordingly, it is difficult to explain the addition patterns by considering the strain and charge density on the cage with a fixed cluster, and thus a moving cluster may account for the addition patterns. These results show that the situation of CCMFs is more complicated than those in other metallofullerenes. Furthermore, a thermal isomerization process from 2b to 2c was observed, confirming that the most abundant isomer 2b is a kinetically favored adduct. Finally, it is revealed that the electronic and electrochemical properties of pristine Sc(2)C(2)@C(2v)(5)-C(80) have been markedly altered by exohedral modification." @default.
• W2334335068 created "2016-06-24" @default.
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• W2334335068 date "2012-02-02" @default.
• W2334335068 modified "2023-10-16" @default.
• W2334335068 title "Chemical Understanding of Carbide Cluster Metallofullerenes: A Case Study on Sc₂C₂@<i>C</i>_2<i>v</i>(5)–C₈₀ with Complete X-ray Crystallographic Characterizations" @default.
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• W2334335068 doi "https://doi.org/10.1021/ja210101f" @default.
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