Stepwise Synthesis of Bis-Alkynyl Co<sup>III</sup>(cyclam) Complexes
under Ambient Conditions
Sean N. Natoli
Matthias Zeller
Tong Ren
10.1021/acs.inorgchem.6b01076.s002
https://acs.figshare.com/articles/dataset/Stepwise_Synthesis_of_Bis-Alkynyl_Co_sup_III_sup_cyclam_Complexes_under_Ambient_Conditions/3420733
Reported
herein is a new synthetic method for the synthesis of Co<sup>III</sup>(cyclam) bis-alkynyls (cyclam = 1,4,8,11-tetraazacyclotetradecane)
under aerobic conditions. Upon the treatment of AgOTf in acetonitrile,
complex <i>trans</i>-[Co(cyclam)(C<sub>2</sub>C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub>)Cl]Cl (<b>1</b>) was converted
to <i>trans</i>-[Co(cyclam)(C<sub>2</sub>C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub>) (NCMe)](OTf)<sub>2</sub> (<b>2</b>),
and <b>2</b> was in turn reacted with HC<sub>2</sub>Ar under
weakly basic conditions to afford the novel bis-alkynyls <i>trans</i>-[Co(cyclam)(C<sub>2</sub>C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub>)(C<sub>2</sub>Ar)](OTf) (Ar = C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub> (<b>3</b>) and C<sub>6</sub>F<sub>5</sub> (<b>4</b>)) in reasonable yields. Voltammetric analysis revealed a modest
NMe<sub>2</sub>/NMe<sub>2</sub> coupling across the Co-alkynyl backbone
in <b>3</b>, while DFT calculations identified the HOMO in <b>3</b> as the superexchange pathway for such coupling.
2016-06-06 19:13:44
Voltammetric analysis
HC 2 Ar
Co III
C 6 H 4 NMe 2
Stepwise Synthesis
C 6 F 5
superexchange pathway
DFT calculations
Ambient Conditions Reported
tran
cyclam
HOMO