Heterocyclic-based ferrocenyl carboselenolates: Synthesis, solid-state structure and electrochemical investigations

Deeb Taher, Firas F. Awwadi, J. Matthaeus Speck, Marcus Korb, Dieter Schaarschmidt, Saddam Weheabby, Almeqdad Y. Habashneh, Mousa Al-Noaimi, Mohammad El-Khateeb, Sultan T. Abu-Orabi, Heinrich Lang

Research output: Contribution to journalArticle

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Abstract

Treatment of two equiv. of [Fe(eta(5)-C5H5)(eta(5)-C5H4SeSiMe3)] (1) with one equiv. of 2,5-(ClC(O))(2)-(C4H2X)-C-c (2) produced the corresponding ferrocenyl carboselenolates 2,5-[(FcSeC(O))(2)-(C4H2X)-C-c] (3) ([Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)]; a, X = O; b, X = NMe; c, X = Se). On the other hand, [Fe(eta 5-C5H4SiMe3)(2)] (4) reacted with 2-ClC(O)-cC4H3X (5) in a 1: 2 M ratio to give [Fe(eta(5)-C5H4SeC(O)-2-(C4H3X)-C-c)(2)] (6) (a, X = O; b, X = NMe; c, X = Se). Compounds 3a-c and 6a-c have been characterized by elemental analysis, NMR (H-1, C-13{H-1}, Se-77{H-1}) and IR spectroscopy. The structures of 3a-c and 6a in the solid state were determined by single crystal X-ray structure analysis. The cyclic voltammetry measurements for 3a-c and 6aec show reversible electrochemical processes (Fc/Fc(+)) between 135 and 170 mV for 3a-c and between 135 and 220 mV for 6a-c using [NnBu(4)][B(C6F5)(4)] as the supporting electrolyte. It was found that the furyl-and selenophyl-functionalized systems resulted in a significantly higher Fc/Fc(+) redox potential (E-0') as observed for the more electron-rich pyrrolyl derivatives. The Fc/Fc(+) redox potential (E-0') for 6a-c is significantly higher than the one for 3a-c, due to the presence of two selenoester moieties attached to the ferrocene in 6a-c. Spectroelectrochemical UVeVis/NIR studies of 3b reveal that the two Fc/Fc(+) centers in the mixed-valent species are not electronically intercommunicating via the heterocyclic bridge. (C) 2017 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)55-62
Number of pages8
JournalJournal of Organometallic Chemistry
Volume845
DOIs
Publication statusPublished - 15 Sep 2017
Externally publishedYes

Cite this

Taher, Deeb ; Awwadi, Firas F. ; Speck, J. Matthaeus ; Korb, Marcus ; Schaarschmidt, Dieter ; Weheabby, Saddam ; Habashneh, Almeqdad Y. ; Al-Noaimi, Mousa ; El-Khateeb, Mohammad ; Abu-Orabi, Sultan T. ; Lang, Heinrich. / Heterocyclic-based ferrocenyl carboselenolates : Synthesis, solid-state structure and electrochemical investigations. In: Journal of Organometallic Chemistry. 2017 ; Vol. 845. pp. 55-62.
@article{5bcef7138f89421e96920dca04ce860e,
title = "Heterocyclic-based ferrocenyl carboselenolates: Synthesis, solid-state structure and electrochemical investigations",
abstract = "Treatment of two equiv. of [Fe(eta(5)-C5H5)(eta(5)-C5H4SeSiMe3)] (1) with one equiv. of 2,5-(ClC(O))(2)-(C4H2X)-C-c (2) produced the corresponding ferrocenyl carboselenolates 2,5-[(FcSeC(O))(2)-(C4H2X)-C-c] (3) ([Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)]; a, X = O; b, X = NMe; c, X = Se). On the other hand, [Fe(eta 5-C5H4SiMe3)(2)] (4) reacted with 2-ClC(O)-cC4H3X (5) in a 1: 2 M ratio to give [Fe(eta(5)-C5H4SeC(O)-2-(C4H3X)-C-c)(2)] (6) (a, X = O; b, X = NMe; c, X = Se). Compounds 3a-c and 6a-c have been characterized by elemental analysis, NMR (H-1, C-13{H-1}, Se-77{H-1}) and IR spectroscopy. The structures of 3a-c and 6a in the solid state were determined by single crystal X-ray structure analysis. The cyclic voltammetry measurements for 3a-c and 6aec show reversible electrochemical processes (Fc/Fc(+)) between 135 and 170 mV for 3a-c and between 135 and 220 mV for 6a-c using [NnBu(4)][B(C6F5)(4)] as the supporting electrolyte. It was found that the furyl-and selenophyl-functionalized systems resulted in a significantly higher Fc/Fc(+) redox potential (E-0') as observed for the more electron-rich pyrrolyl derivatives. The Fc/Fc(+) redox potential (E-0') for 6a-c is significantly higher than the one for 3a-c, due to the presence of two selenoester moieties attached to the ferrocene in 6a-c. Spectroelectrochemical UVeVis/NIR studies of 3b reveal that the two Fc/Fc(+) centers in the mixed-valent species are not electronically intercommunicating via the heterocyclic bridge. (C) 2017 Elsevier B.V. All rights reserved.",
keywords = "Ferrocene, Selenoester, Pyrrole, Furan, Solid state structure, Electrochemistry, METAL-METAL INTERACTIONS, CYCLIC VOLTAMMETRY, CHARGE-TRANSFER, ELECTRONIC-STRUCTURE, NONAQUEOUS SOLVENTS, DELTA-E-1/2 VALUES, MOLECULAR WIRES, COMPLEXES, CHEMISTRY, METALLOCENES",
author = "Deeb Taher and Awwadi, {Firas F.} and Speck, {J. Matthaeus} and Marcus Korb and Dieter Schaarschmidt and Saddam Weheabby and Habashneh, {Almeqdad Y.} and Mousa Al-Noaimi and Mohammad El-Khateeb and Abu-Orabi, {Sultan T.} and Heinrich Lang",
year = "2017",
month = "9",
day = "15",
doi = "10.1016/j.jorganchem.2017.02.024",
language = "English",
volume = "845",
pages = "55--62",
journal = "Journal of Organometallic Chemistry",
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publisher = "Elsevier Science & Technology",

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Taher, D, Awwadi, FF, Speck, JM, Korb, M, Schaarschmidt, D, Weheabby, S, Habashneh, AY, Al-Noaimi, M, El-Khateeb, M, Abu-Orabi, ST & Lang, H 2017, 'Heterocyclic-based ferrocenyl carboselenolates: Synthesis, solid-state structure and electrochemical investigations' Journal of Organometallic Chemistry, vol. 845, pp. 55-62. https://doi.org/10.1016/j.jorganchem.2017.02.024

Heterocyclic-based ferrocenyl carboselenolates : Synthesis, solid-state structure and electrochemical investigations. / Taher, Deeb; Awwadi, Firas F.; Speck, J. Matthaeus; Korb, Marcus; Schaarschmidt, Dieter; Weheabby, Saddam; Habashneh, Almeqdad Y.; Al-Noaimi, Mousa; El-Khateeb, Mohammad; Abu-Orabi, Sultan T.; Lang, Heinrich.

In: Journal of Organometallic Chemistry, Vol. 845, 15.09.2017, p. 55-62.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Heterocyclic-based ferrocenyl carboselenolates

T2 - Synthesis, solid-state structure and electrochemical investigations

AU - Taher, Deeb

AU - Awwadi, Firas F.

AU - Speck, J. Matthaeus

AU - Korb, Marcus

AU - Schaarschmidt, Dieter

AU - Weheabby, Saddam

AU - Habashneh, Almeqdad Y.

AU - Al-Noaimi, Mousa

AU - El-Khateeb, Mohammad

AU - Abu-Orabi, Sultan T.

AU - Lang, Heinrich

PY - 2017/9/15

Y1 - 2017/9/15

N2 - Treatment of two equiv. of [Fe(eta(5)-C5H5)(eta(5)-C5H4SeSiMe3)] (1) with one equiv. of 2,5-(ClC(O))(2)-(C4H2X)-C-c (2) produced the corresponding ferrocenyl carboselenolates 2,5-[(FcSeC(O))(2)-(C4H2X)-C-c] (3) ([Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)]; a, X = O; b, X = NMe; c, X = Se). On the other hand, [Fe(eta 5-C5H4SiMe3)(2)] (4) reacted with 2-ClC(O)-cC4H3X (5) in a 1: 2 M ratio to give [Fe(eta(5)-C5H4SeC(O)-2-(C4H3X)-C-c)(2)] (6) (a, X = O; b, X = NMe; c, X = Se). Compounds 3a-c and 6a-c have been characterized by elemental analysis, NMR (H-1, C-13{H-1}, Se-77{H-1}) and IR spectroscopy. The structures of 3a-c and 6a in the solid state were determined by single crystal X-ray structure analysis. The cyclic voltammetry measurements for 3a-c and 6aec show reversible electrochemical processes (Fc/Fc(+)) between 135 and 170 mV for 3a-c and between 135 and 220 mV for 6a-c using [NnBu(4)][B(C6F5)(4)] as the supporting electrolyte. It was found that the furyl-and selenophyl-functionalized systems resulted in a significantly higher Fc/Fc(+) redox potential (E-0') as observed for the more electron-rich pyrrolyl derivatives. The Fc/Fc(+) redox potential (E-0') for 6a-c is significantly higher than the one for 3a-c, due to the presence of two selenoester moieties attached to the ferrocene in 6a-c. Spectroelectrochemical UVeVis/NIR studies of 3b reveal that the two Fc/Fc(+) centers in the mixed-valent species are not electronically intercommunicating via the heterocyclic bridge. (C) 2017 Elsevier B.V. All rights reserved.

AB - Treatment of two equiv. of [Fe(eta(5)-C5H5)(eta(5)-C5H4SeSiMe3)] (1) with one equiv. of 2,5-(ClC(O))(2)-(C4H2X)-C-c (2) produced the corresponding ferrocenyl carboselenolates 2,5-[(FcSeC(O))(2)-(C4H2X)-C-c] (3) ([Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)]; a, X = O; b, X = NMe; c, X = Se). On the other hand, [Fe(eta 5-C5H4SiMe3)(2)] (4) reacted with 2-ClC(O)-cC4H3X (5) in a 1: 2 M ratio to give [Fe(eta(5)-C5H4SeC(O)-2-(C4H3X)-C-c)(2)] (6) (a, X = O; b, X = NMe; c, X = Se). Compounds 3a-c and 6a-c have been characterized by elemental analysis, NMR (H-1, C-13{H-1}, Se-77{H-1}) and IR spectroscopy. The structures of 3a-c and 6a in the solid state were determined by single crystal X-ray structure analysis. The cyclic voltammetry measurements for 3a-c and 6aec show reversible electrochemical processes (Fc/Fc(+)) between 135 and 170 mV for 3a-c and between 135 and 220 mV for 6a-c using [NnBu(4)][B(C6F5)(4)] as the supporting electrolyte. It was found that the furyl-and selenophyl-functionalized systems resulted in a significantly higher Fc/Fc(+) redox potential (E-0') as observed for the more electron-rich pyrrolyl derivatives. The Fc/Fc(+) redox potential (E-0') for 6a-c is significantly higher than the one for 3a-c, due to the presence of two selenoester moieties attached to the ferrocene in 6a-c. Spectroelectrochemical UVeVis/NIR studies of 3b reveal that the two Fc/Fc(+) centers in the mixed-valent species are not electronically intercommunicating via the heterocyclic bridge. (C) 2017 Elsevier B.V. All rights reserved.

KW - Ferrocene

KW - Selenoester

KW - Pyrrole

KW - Furan

KW - Solid state structure

KW - Electrochemistry

KW - METAL-METAL INTERACTIONS

KW - CYCLIC VOLTAMMETRY

KW - CHARGE-TRANSFER

KW - ELECTRONIC-STRUCTURE

KW - NONAQUEOUS SOLVENTS

KW - DELTA-E-1/2 VALUES

KW - MOLECULAR WIRES

KW - COMPLEXES

KW - CHEMISTRY

KW - METALLOCENES

U2 - 10.1016/j.jorganchem.2017.02.024

DO - 10.1016/j.jorganchem.2017.02.024

M3 - Article

VL - 845

SP - 55

EP - 62

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -