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

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• 作者：Sean N. Natoli ; Matthias Zeller ; Tong Ren
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：June 20, 2016
• 年：2016
• 卷：55
• 期：12
• 页码：5756-5758
• 全文大小：249K
• 年卷期：0
• ISSN：1520-510X

文摘

Reported herein is a new synthetic method for the synthesis of Co^III(cyclam) bis-alkynyls (cyclam = 1,4,8,11-tetraazacyclotetradecane) 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)](OTf)₂ (2), and 2 was in turn reacted with HC₂Ar under weakly basic conditions to afford the novel bis-alkynyls trans-[Co(cyclam)(C₂C₆H₄NMe₂)(C₂Ar)](OTf) (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.