Syntheses and structural characterization of some mono- and di- p-nitrophenyl[3]ferrocenophanes: X-ray structure of [3]ferrocenophane, 3- p-nitrophenyl[3]ferrocenophane, and 3,4′-bis-( p-nitrophenyl)[3]ferrocenophane; DFT calculations on ferrocene derivatives

• Published in: Journal of organometallic chemistry 2002-04, Vol.649 (2), p.161-172
• Main Authors: Kadkin, Oleg, Näther, Christian, Friedrichsen, Willy
• Format: Article
• Language: English
• Subjects: Bridged ferrocenes; DFT calculations; Ferrocenophane; Gomberg arylation reaction
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/S0022-328X(02)01113-0

[3]Ferrocenophane ( 3a) reacts in a Gomberg reaction with diazotized p-nitroaniline to give a mixture of mono- and di-substituted products. The isomeric pairs of 3- and 2-( p-nitrophenyl)[3]ferrocenophanes ( 4 and 5), as well as 3,4′- and 3,4- bis-( p-nitrophenyl)[3]ferrocenophanes ( 6 and 7) were separated from the mixture by column chromatography on Al 2O 3 and characterized by means of mass, IR, UV, 1H-NMR spectroscopy, and by X-ray analysis ( 4 and 6). PM3/tm and density functional theoretical calculations on ferrocene ( 1) and ferrocenophane derivatives are reported. A refined X-ray structure determination of [3]ferrocenophane ( 3a) is given. The Gomberg reaction of [3]ferrocenophane with diazotized p-nitroaniline led to mono- and di-arylated [3]ferrocenophanes. The structures of 3-( p-nitrophenyl)[3]ferrocenophane and 3,4′- bis-( p-nitrophenyl)[3]ferrocenophane have been clarified by X-ray structure determinations. A revised crystal structure determination of [3]ferrocenopahne is reported. DFT studies of various [3]ferrocenophanes are in good agreement with experimental data.