How Strained are [1]Ferrocenophanes?

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• 作者：Elaheh Khozeimeh Sarbisheh ; Hridaynath Bhattacharjee ; My Phan Thuy Cao ; Jianfeng Zhu ; Jens Müller
• 刊名：Organometallics
• 出版年：2017
• 出版时间：February 13, 2017
• 年：2017
• 卷：36
• 期：3
• 页码：614-621
• 全文大小：434K
• ISSN：1520-6041

文摘

A series of [1]ferrocenophanes ([1]FCPs) bridged by boron, carbon, silicon, phosphorus, and sulfur, respectively, were investigated by DFT calculations. A comparison of measured molecular structures with calculated structures showed that the applied B3PW91/6-311+G(d,p) level of theory provides realistic molecular geometries. Geometry optimization of carbon-bridged [1]FCPs (ER_x = CH₂, CMe₂) revealed that these unknown species with tilt angles α of 38.5° may be sufficiently stable to allow isolation, given sufficient kinetic stability. In order to measure the amount of strain in [1]FCPs, a hypothetical 1,2-addition of a C–H group of FeCp₂ across the E–C^ipso bond of a [1]FCP to give a bis(ferrocenyl)species was investigated. The calculated reaction enthalpies were compared to experimental ΔH^ROP values as obtained from differential scanning calorimetry (DSC) measurements.