From ferrocenyl selenoesters to diferrocenyl methanols

Deeb Taher, Firas F. Awwadi, J. Matthaeus Speck, Marcus Korb, Dieter Schaarschmidt, Christoph Wagner, Hazem Amarne, Kurt Merzweiler, Gerard van Koten, Heinrich Lang

Research output: Contribution to journalArticle

4 Citations (Scopus)

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 languageEnglish
Pages (from-to)1-9
Number of pages9
JournalJournal of Organometallic Chemistry
Volume863
DOIs
Publication statusPublished - 15 May 2018
Externally publishedYes

Cite this

Taher, D., Awwadi, F. F., Speck, J. M., Korb, M., Schaarschmidt, D., Wagner, C., ... Lang, H. (2018). From ferrocenyl selenoesters to diferrocenyl methanols. Journal of Organometallic Chemistry, 863, 1-9. https://doi.org/10.1016/j.jorganchem.2018.02.006
Taher, Deeb ; Awwadi, Firas F. ; Speck, J. Matthaeus ; Korb, Marcus ; Schaarschmidt, Dieter ; Wagner, Christoph ; Amarne, Hazem ; Merzweiler, Kurt ; van Koten, Gerard ; Lang, Heinrich. / From ferrocenyl selenoesters to diferrocenyl methanols. In: Journal of Organometallic Chemistry. 2018 ; Vol. 863. pp. 1-9.
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title = "From ferrocenyl selenoesters to diferrocenyl methanols",
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.",
keywords = "Selenoester, Ferrocene, N-Methyl pyrrole, Furan, Electrochemistry, Solid state structure, SOLID-STATE STRUCTURE, METAL-METAL INTERACTIONS, ELECTROCHEMICAL INVESTIGATIONS, CYCLIC VOLTAMMETRY, NONAQUEOUS SOLVENTS, DELTA-E-1/2 VALUES, ELECTRON-TRANSFER, MOLECULAR WIRES, REDOX BEHAVIOR, COMPLEXES",
author = "Deeb Taher and Awwadi, {Firas F.} and Speck, {J. Matthaeus} and Marcus Korb and Dieter Schaarschmidt and Christoph Wagner and Hazem Amarne and Kurt Merzweiler and {van Koten}, Gerard and Heinrich Lang",
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Taher, D, Awwadi, FF, Speck, JM, Korb, M, Schaarschmidt, D, Wagner, C, Amarne, H, Merzweiler, K, van Koten, G & Lang, H 2018, 'From ferrocenyl selenoesters to diferrocenyl methanols' Journal of Organometallic Chemistry, vol. 863, pp. 1-9. https://doi.org/10.1016/j.jorganchem.2018.02.006

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 journalArticle

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 -