Sc<sub>2</sub>C<sub>2</sub>@C<sub>80</sub> Rather than Sc<sub>2</sub>@C<sub>82</sub>: Templated Formation of Unexpected <i>C</i><sub>2<i>v</i></sub>(5)-C<sub>80</sub> and Temperature-Dependent Dynamic Motion of Internal Sc<sub>2</sub>C<sub>2</sub> Cluster
Hiroki Kurihara (265457)Xing Lu (1438414)Yuko Iiduka (2113522)Naomi Mizorogi (1775047)Zdenek Slanina (1689757)Takahiro Tsuchiya (2015767)Takeshi Akasaka (1402213)Shigeru Nagase (1349634)
Abstract
Unambiguous X-ray crystallographic results of the carbene adduct of Sc<sub>2</sub>C<sub>82</sub> reveal a new carbide cluster metallofullerene with the unexpected <i>C</i><sub>2<i>v</i></sub>(5)-C<sub>80</sub> cage, that is, Sc<sub>2</sub>C<sub>2</sub><i>@C</i><sub>2<i>v</i></sub>(5)-C<sub>80</sub>. More interestingly, DFT calculations and NMR results disclose that the dynamic motion of the internal Sc<sub>2</sub>C<sub>2</sub> cluster depends strongly on temperature. At 293 K, the cluster is fixed inside the cage with two nonequivalent Sc atoms on the mirror plane, thereby leading to <i>C</i><sub><i>s</i></sub> symmetry of the whole molecule. However, when the temperature increases to 413 K, the <sup>13</sup>C and <sup>45</sup>Sc NMR spectra show that the cluster rotates rapidly inside the <i>C</i><sub>2<i>v</i></sub>(5)-C<sub>80</sub> cage, featuring two equivalent Sc atoms and weaker metal−cage interactions.
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