%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)5-η1-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