New Fe(III)(cyclam) Complexes Bearing Axially Bound geminal-Diethynylethenes

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• 作者：Zhi Cao ; Phillip E. Fanwick ; William P. Forrest ; Yang Gao ; Tong Ren
• 刊名：Organometallics
• 出版年：2013
• 出版时间：August 26, 2013
• 年：2013
• 卷：32
• 期：16
• 页码：4684-4689
• 全文大小：304K
• 年卷期：v.32,no.16(August 26, 2013)
• ISSN：1520-6041

文摘

Reported herein are the preparation and characterization of trans-[Fe(cyclam)(X-gem-DEE)₂]OTf (where cyclam = 1,4,8,11-tetraazacyclotetradecane, gem-DEE = 蟽-geminal-diethynylethene, and OTf = trifluoromethanesulfonate) compounds 2a, 2b, and 2c (X = 鈭扨h (2a), 鈭扴ip>ip>Pr₃ (2b), and 鈭扚c (2c)), which are the first examples of redox-active 3d metal complexes containing gem-DEE ligands. These compounds were prepared from the reaction between cis/trans-[Fe(cyclam)(OTf)₂]OTf (1) and X-gem-DEE-Li. Compounds 2a鈥?b>2c were characterized by spectroscopic/voltammetric techniques. The trans-orientation of the gem-DEE ligands was established from the single-crystal X-ray diffraction study of 2a. Furthermore, the electronic structures of the model compounds 2a鈥?sup>+p> and 2b鈥?sup>+p> were analyzed with density-functional-theory calculations, which revealed significant d蟺(Fe)鈭捪€(gem-DEE) interactions.