Abstract
A series of 1,1′-ferrocenyldiimines [Fe{(η5-C5H4)-C(Me)N-R}2 ], where R = n-hexyl 1a, cyclohexyl 1b, phenyl 1c, 4-methoxyphenyl 1d, 3-methoxyphenyl 1e, 4-nitrophenyl 1f, and 3-nitrophenyl 1g, have been synthesized by reactions of ca. 1:2 M ratio of 1,1′-diacetylferrocene and the corresponding amines. While ca. 1:1 M ratio of the starting materials was employed, acetylferrocenylimines [Fe{(η5-C5H4)-C(CH3){dou ble bond, long}O}{(η5-C5H4)-C(CH3) {double bond, long}N-R}], where R = 4-nitrophenyl 2f, and 3-nitrophenyl 2g, were obtained. Single crystal X-ray structural analysis revealed that the two cyclopentadienyl rings in 1d, 1e, 1g, 2f, and 2g were antiperiplanar staggered, anticlinal eclipsed, anticlinal eclipsed/synclinal eclipsed, synclinal eclipsed, and synclinal eclipsed to each other in solid state, respectively. All synthesized ferrocene derivatives exhibited a reversible one-electron redox process in their cyclic voltammograms, and the values of their redox potentials relied on the R groups. The correlation between the redox potential and the Hammett substituent constant, σp was quite well, with a correlation coefficient of 0.98. The UV-vis spectra showed that their optical property was also substituent dependent.
| Original language | English |
|---|---|
| Pages (from-to) | 102-109 |
| Number of pages | 8 |
| Journal | Journal of Molecular Structure |
| Volume | 935 |
| Issue number | 1-3 |
| DOIs | |
| Publication status | Published - 2009 Oct 29 |
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All Science Journal Classification (ASJC) codes
- Analytical Chemistry
- Spectroscopy
- Organic Chemistry
- Inorganic Chemistry
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From diacetylferrocene to 1,1′-ferrocenyldiimines : Substituent effects on synthesis, molecular structure, electrochemical behavior and optical absorption property. / Lee, Ting Yu; Chiang, Pui Ren; Tsai, Ming Chen; Lin, Che Yu; Huang, Jui-Hsien.
In: Journal of Molecular Structure, Vol. 935, No. 1-3, 29.10.2009, p. 102-109.Research output: Contribution to journal › Article
TY - JOUR
T1 - From diacetylferrocene to 1,1′-ferrocenyldiimines
T2 - Substituent effects on synthesis, molecular structure, electrochemical behavior and optical absorption property
AU - Lee, Ting Yu
AU - Chiang, Pui Ren
AU - Tsai, Ming Chen
AU - Lin, Che Yu
AU - Huang, Jui-Hsien
PY - 2009/10/29
Y1 - 2009/10/29
N2 - A series of 1,1′-ferrocenyldiimines [Fe{(η5-C5H4)-C(Me)N-R}2 ], where R = n-hexyl 1a, cyclohexyl 1b, phenyl 1c, 4-methoxyphenyl 1d, 3-methoxyphenyl 1e, 4-nitrophenyl 1f, and 3-nitrophenyl 1g, have been synthesized by reactions of ca. 1:2 M ratio of 1,1′-diacetylferrocene and the corresponding amines. While ca. 1:1 M ratio of the starting materials was employed, acetylferrocenylimines [Fe{(η5-C5H4)-C(CH3){dou ble bond, long}O}{(η5-C5H4)-C(CH3) {double bond, long}N-R}], where R = 4-nitrophenyl 2f, and 3-nitrophenyl 2g, were obtained. Single crystal X-ray structural analysis revealed that the two cyclopentadienyl rings in 1d, 1e, 1g, 2f, and 2g were antiperiplanar staggered, anticlinal eclipsed, anticlinal eclipsed/synclinal eclipsed, synclinal eclipsed, and synclinal eclipsed to each other in solid state, respectively. All synthesized ferrocene derivatives exhibited a reversible one-electron redox process in their cyclic voltammograms, and the values of their redox potentials relied on the R groups. The correlation between the redox potential and the Hammett substituent constant, σp was quite well, with a correlation coefficient of 0.98. The UV-vis spectra showed that their optical property was also substituent dependent.
AB - A series of 1,1′-ferrocenyldiimines [Fe{(η5-C5H4)-C(Me)N-R}2 ], where R = n-hexyl 1a, cyclohexyl 1b, phenyl 1c, 4-methoxyphenyl 1d, 3-methoxyphenyl 1e, 4-nitrophenyl 1f, and 3-nitrophenyl 1g, have been synthesized by reactions of ca. 1:2 M ratio of 1,1′-diacetylferrocene and the corresponding amines. While ca. 1:1 M ratio of the starting materials was employed, acetylferrocenylimines [Fe{(η5-C5H4)-C(CH3){dou ble bond, long}O}{(η5-C5H4)-C(CH3) {double bond, long}N-R}], where R = 4-nitrophenyl 2f, and 3-nitrophenyl 2g, were obtained. Single crystal X-ray structural analysis revealed that the two cyclopentadienyl rings in 1d, 1e, 1g, 2f, and 2g were antiperiplanar staggered, anticlinal eclipsed, anticlinal eclipsed/synclinal eclipsed, synclinal eclipsed, and synclinal eclipsed to each other in solid state, respectively. All synthesized ferrocene derivatives exhibited a reversible one-electron redox process in their cyclic voltammograms, and the values of their redox potentials relied on the R groups. The correlation between the redox potential and the Hammett substituent constant, σp was quite well, with a correlation coefficient of 0.98. The UV-vis spectra showed that their optical property was also substituent dependent.
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U2 - 10.1016/j.molstruc.2009.06.047
DO - 10.1016/j.molstruc.2009.06.047
M3 - Article
AN - SCOPUS:69649086507
VL - 935
SP - 102
EP - 109
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
SN - 0022-2860
IS - 1-3
ER -