| Summary: | The reactivity of the open-shell Gd@<i>C</i><sub>2v</sub>-C<sub>82</sub> with different charge states towards benzyl bromide was investigated. [Gd@<i>C</i><sub>2v</sub>-C<sub>82</sub>]<sup>3−</sup> exhibited enhanced activity relative to Gd@<i>C</i><sub>2v</sub>-C<sub>82</sub> and [Gd@<i>C</i><sub>2v</sub>-C<sub>82</sub>]<sup>−</sup>. The structural characterizations, including MALDI-TOF MS, UV-vis-NIR, and single crystal X-ray diffraction, indicate the formation of isomeric benzyl monoadducts of Gd@<i>C</i><sub>2v</sub>-C<sub>82</sub>. All three monoadducts contain 1:1 mirror-symmetric enantiomers. Additionally, the addition of the benzyl group and its specific position result in distinct electrochemical behavior of the products compared to the parent Gd@<i>C</i><sub>2v</sub>-C<sub>82</sub>. Theoretical studies demonstrate that only [Gd@<i>C</i><sub>2v</sub>-C<sub>82</sub>]<sup>3−</sup> has a HOMO energy level that matches well with the LUMO energy level of the PhCH<sub>2</sub> radical, providing a rationalization for the observed significantly different reactivity.
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