J. Speck, Dieter Schaarschmidt, H. Lang
Feb 27, 2012
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0
Influential Citations
49
Citations
Journal
Organometallics
Abstract
3,3′,4,4′,5,5′-Hexaferrocenyl-2,2′-bithiophene (4) has been prepared using a straightforward synthesis protocol that follows the palladium-promoted Negishi cross-coupling of 2-Br-3,4,5-Fc3-cC4S (2) with 3,4,5-Fc3-2-ZnCl-cC4S (3) (Fc = Fe(η5-C5H4)(η5-C5H5)). The electronic and structural properties of 4 were investigated by UV–vis spectroscopy and single-crystal X-ray diffraction studies. Comparison of the appropriate bond distances in the 2,2′-bithiophene moiety shows electron delocalization. Cyclic and square-wave voltammetry and in situ UV–vis/NIR spectroelectrochemistry highlight the electrochemical properties of 4. The ferrocenyls in 4 can be reversibly and separately oxidized in dichloromethane and anisole solutions using [NnBu4][B(C6F5)4] as supporting electrolyte. Generally, these studies prove electrostatic interactions among the ferrocenyl termini as oxidation progresses. The atropisomerism of 4 caused by the inner rotation barrier about the 2,2′-bithiophene bond was investigated by dynamic 1H NM...