%0 Journal Article %A Xie, Yun-Peng %A Pan, Changwang %A Bao, Lipiao %A Slanina, Zdenek %A Akasaka, Takeshi %A Lu, Xing %D 2019 %T Regioselective Coordination of Re2(CO)10 to Y@C2v(9)‑C82: An Unprecedented η1 Complex Stabilized by Intramolecular Electron Transfer %U https://acs.figshare.com/articles/journal_contribution/Regioselective_Coordination_of_Re_sub_2_sub_CO_sub_10_sub_to_Y_C_sub_2v_sub_9_C_sub_82_sub_An_Unprecedented_sup_1_sup_Complex_Stabilized_by_Intramolecular_Electron_Transfer/8061446 %R 10.1021/acs.organomet.9b00209.s001 %2 https://acs.figshare.com/ndownloader/files/15023006 %K stability %K Re %K EMF %K rhenium moiety coordinates %K Unprecedented η 1 Complex Stabilized %K η 1 %K CO %K metallofullerene %K electrochemical %K Intramolecular Electron Transfer %K ESR %X The prototypical η1-coordinated complexes of endohedral metallofullerenes (EMFs) have never been reported because of their low stability. Herein, we have developed a highly efficient radical-coupling strategy by performing a regioselective photochemical reaction of a rhenium complex (1) with the paramagnetic Y@C2v(9)-C82 to form an unprecedented η1-coordinated complex with high stability: namely, Re­(CO)51-Y@C2v(9)-C82 (2). X-ray results demonstrate that the rhenium moiety coordinates to a [5,6,6]-carbon atom on the cage via a single Re–C σ bond. Vis–NIR results suggest that 2 displays an absorption curve that is identical with the monoanion of metallofullerene [Y@C2v(9)-C82], confirming unambiguously that one electron is transferred from the rhenium center to Y@C2v(9)-C82. This is also confirmed by an ESR study showing the diamagnetic properties of 2. Surprisingly, our electrochemical results reveal that 2 possesses a redox behavior similar to that of pristine Y@C2v(9)-C82. Thus, we have presented a useful methodology for the synthesis of EMF-based molecular building blocks with the same electrochemical properties but different electronic configurations (e.g., open shell versus closed shell). %I ACS Publications