Unsymmetric Mononuclear and Bridged Dinuclear CoIII(cyclam) Acetylides

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• 作者：Timothy D. Cook ; Phillip E. Fanwick ; Tong Ren
• 刊名：Organometallics
• 出版年：2014
• 出版时间：September 22, 2014
• 年：2014
• 卷：33
• 期：18
• 页码：4621-4624
• 全文大小：341K
• ISSN：1520-6041

文摘

Reported herein are the preparation and characterization of a new trans-bis(acetylide) complex of Co^III(cyclam) (cyclam = 1,4,8,11-tetraazacyclotetradecane) bearing two different acetylide ligands (1) and the first example of an all-carbon (C₄) bridged dinuclear Co species (2). Structural features of monomeric 1 and dimeric 2 are similar to those of the previously reported Co^III(cyclam) bis(acetylides), and the C鈮 and C鈥揅 bond lengths of the butadiynediyl bridge in 2 conform to the acetylenic resonance form. The Co centers in the bridged complex 2 do not exhibit a measurable electronic coupling, as revealed by voltammetric measurements, and this behavior is rationalized through the DFT analysis of complexes 1 and 2.