Abstract
The reaction of FcSeSiMe(3) (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)) (1) with equimolar amounts of the acid chlorides Cl(O) C-2-(C4H3X)-C-c (2a, X = O; 2b, X = NMe) gave the ferrocenyl selenoesters FcSe(C(O)-2-(C4H3X)-C-c) (3a, X = O; 3b, X = NMe). Upon exposure to silica gel compounds both 3a and 3b underwent an intermolecular conversion followed by transesterification with the silica surface to afford diferrocenyl methanols Fc(2)C(OH)(2-(C4H3X)-C-c) (4a, X = O; 4b, X = NMe). Compounds 3a, 3b, 4a and 4b have been characterized by elemental analysis, IR and NMR (H-1, C-13{H-1}, Se-77{H-1}) spectroscopy and ESI-TOF mass spectrometry (4a and 4b). The molecular structures of 3a, 4a and 4b in the solid state were determined by single crystal Xray diffraction studies. The electrochemical studies exhibit for 3a and 3b reversible one-electron Fc/Fcthorn redox processes. During the electrochemical investigations of 4a and 4b two well-separated one-electron redox events could be determined (4a, Delta E0' = 330mV; 4b, 367 mV). UV-Vis/NIR spectroelectrochemical studies on 4a and 4b reveal a weak electronic coupling between the iron centers in the corresponding mixed-valent species of [4a] thorn and [4b] thorn according to Robin and Day classification. (c) 2018 Elsevier B.V. All rights reserved.
| Original language | English |
|---|---|
| Pages (from-to) | 1-9 |
| Number of pages | 9 |
| Journal | Journal of Organometallic Chemistry |
| Volume | 863 |
| DOIs | |
| Publication status | Published - 15 May 2018 |
| Externally published | Yes |
Cite this
}
From ferrocenyl selenoesters to diferrocenyl methanols. / Taher, Deeb; Awwadi, Firas F.; Speck, J. Matthaeus; Korb, Marcus; Schaarschmidt, Dieter; Wagner, Christoph; Amarne, Hazem; Merzweiler, Kurt; van Koten, Gerard; Lang, Heinrich.
In: Journal of Organometallic Chemistry, Vol. 863, 15.05.2018, p. 1-9.Research output: Contribution to journal › Article
TY - JOUR
T1 - From ferrocenyl selenoesters to diferrocenyl methanols
AU - Taher, Deeb
AU - Awwadi, Firas F.
AU - Speck, J. Matthaeus
AU - Korb, Marcus
AU - Schaarschmidt, Dieter
AU - Wagner, Christoph
AU - Amarne, Hazem
AU - Merzweiler, Kurt
AU - van Koten, Gerard
AU - Lang, Heinrich
PY - 2018/5/15
Y1 - 2018/5/15
N2 - The reaction of FcSeSiMe(3) (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)) (1) with equimolar amounts of the acid chlorides Cl(O) C-2-(C4H3X)-C-c (2a, X = O; 2b, X = NMe) gave the ferrocenyl selenoesters FcSe(C(O)-2-(C4H3X)-C-c) (3a, X = O; 3b, X = NMe). Upon exposure to silica gel compounds both 3a and 3b underwent an intermolecular conversion followed by transesterification with the silica surface to afford diferrocenyl methanols Fc(2)C(OH)(2-(C4H3X)-C-c) (4a, X = O; 4b, X = NMe). Compounds 3a, 3b, 4a and 4b have been characterized by elemental analysis, IR and NMR (H-1, C-13{H-1}, Se-77{H-1}) spectroscopy and ESI-TOF mass spectrometry (4a and 4b). The molecular structures of 3a, 4a and 4b in the solid state were determined by single crystal Xray diffraction studies. The electrochemical studies exhibit for 3a and 3b reversible one-electron Fc/Fcthorn redox processes. During the electrochemical investigations of 4a and 4b two well-separated one-electron redox events could be determined (4a, Delta E0' = 330mV; 4b, 367 mV). UV-Vis/NIR spectroelectrochemical studies on 4a and 4b reveal a weak electronic coupling between the iron centers in the corresponding mixed-valent species of [4a] thorn and [4b] thorn according to Robin and Day classification. (c) 2018 Elsevier B.V. All rights reserved.
AB - The reaction of FcSeSiMe(3) (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)) (1) with equimolar amounts of the acid chlorides Cl(O) C-2-(C4H3X)-C-c (2a, X = O; 2b, X = NMe) gave the ferrocenyl selenoesters FcSe(C(O)-2-(C4H3X)-C-c) (3a, X = O; 3b, X = NMe). Upon exposure to silica gel compounds both 3a and 3b underwent an intermolecular conversion followed by transesterification with the silica surface to afford diferrocenyl methanols Fc(2)C(OH)(2-(C4H3X)-C-c) (4a, X = O; 4b, X = NMe). Compounds 3a, 3b, 4a and 4b have been characterized by elemental analysis, IR and NMR (H-1, C-13{H-1}, Se-77{H-1}) spectroscopy and ESI-TOF mass spectrometry (4a and 4b). The molecular structures of 3a, 4a and 4b in the solid state were determined by single crystal Xray diffraction studies. The electrochemical studies exhibit for 3a and 3b reversible one-electron Fc/Fcthorn redox processes. During the electrochemical investigations of 4a and 4b two well-separated one-electron redox events could be determined (4a, Delta E0' = 330mV; 4b, 367 mV). UV-Vis/NIR spectroelectrochemical studies on 4a and 4b reveal a weak electronic coupling between the iron centers in the corresponding mixed-valent species of [4a] thorn and [4b] thorn according to Robin and Day classification. (c) 2018 Elsevier B.V. All rights reserved.
KW - Selenoester
KW - Ferrocene
KW - N-Methyl pyrrole
KW - Furan
KW - Electrochemistry
KW - Solid state structure
KW - SOLID-STATE STRUCTURE
KW - METAL-METAL INTERACTIONS
KW - ELECTROCHEMICAL INVESTIGATIONS
KW - CYCLIC VOLTAMMETRY
KW - NONAQUEOUS SOLVENTS
KW - DELTA-E-1/2 VALUES
KW - ELECTRON-TRANSFER
KW - MOLECULAR WIRES
KW - REDOX BEHAVIOR
KW - COMPLEXES
U2 - 10.1016/j.jorganchem.2018.02.006
DO - 10.1016/j.jorganchem.2018.02.006
M3 - Article
VL - 863
SP - 1
EP - 9
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
ER -