Exceptional Chemical Properties
of Sc@<i>C</i><sub>2<i>v</i></sub>(9)–C<sub>82</sub> Probed with
Adamantylidene Carbene
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Abstract
It has been an interesting finding that reactions of
M@<i>C</i><sub>2<i>v</i></sub>(9)–C<sub>82</sub> (M = Y, La, Ce, Gd) with diazirine adamantylidene (AdN<sub>2</sub>, <b>1</b>) gave rise to only two monoadduct isomers,
indicating
that the cage reactivity of monometallofullerenes is not dependent
on the type of the internal metal. However, we found here that Sc@<i>C</i><sub>2<i>v</i></sub>(9)–C<sub>82</sub> shows an exceptional chemical reactivity toward the electrophile <b>1</b>, affording four monoadduct isomers (<b>2a</b>–<b>d</b>). Single-crystal X-ray diffraction crystallographic results
of the most abundant isomer (<b>2a</b>) confirm that the addition
takes place at a [6,6]-bond junction which is very close to the internal
metal ion. Theoretical calculations reveal that 2 out of the 24 nonequivalent
cage carbons of Sc@<i>C</i><sub>2<i>v</i></sub>(9)–C<sub>82</sub> are highly reactive toward <b>1</b>, but only one cage carbon of the other M@<i>C</i><sub>2<i>v</i></sub>–C<sub>82</sub> (M = Y, La, Ce, Gd)
is sufficiently reactive. The exceptional chemical property of Sc@<i>C</i><sub>2<i>v</i></sub>(9)–C<sub>82</sub> is associated with the small ionic radius of Sc<sup>3+</sup>, which
allows stronger metal–cage interactions and makes back-donation
of charge from the cage to the metal more pronounced. Our results
have provided new insights into the art of altering the chemical properties
of fullerene molecules at the atomic level, which would be useful
in the future in utilizing EMFs in quantum computing systems