Stepwise Synthesis of Bis-Alkynyl Co-III(cyclam) Complexes under Ambient Conditions

作者：Natoli Sean N; Zeller Matthias; Ren Tong^*

来源：Inorganic Chemistry, 2016, 55(12): 5756-5758.

DOI：10.1021/acs.inorgchem.6b01076

Reported herein is a new synthetic method for the synthesis of Co-III(cyclam) bis-alkynyls (cyclam = 1,4,8,11-tetraazacydotetradecane) under aerobic conditions. Upon the treatment of AgOTf in acetonitrile, complex trans-[Co (cyclam)(C2C6H4NMe2)Cl] Cl (1) was converted to trans-[Co(cyclam)(C2C6H4NMe2) (NCMe)ROTO2 (2), and 2 was in turn reacted with HC2Ar under weakly basic conditions to afford the novel bis-alkynyls trans-[Co (cydam) (C2C6H4NMe2) ( C2Ar)] - (OTO (Ar = C6H4NMe2 (3) and C6F5 (4)) in reasonable yields. Voltammetric analysis revealed a modest NMe2/NMe2 coupling across the Co-alkynyl backbone in 3, while DFT calculations identified the HOMO in 3 as the superexchange pathway for such coupling.

• 出版日期2016-6-20