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