Ferrocenylmethyl-functionalized 5-membered heterocycles: Synthesis, solid-state structure and electrochemical investigations

Deeb Taher, Asma Ghazzy, Firas F. Awwadi, Wissam Helal, Khaled Al Khalyfeh, Marcus Korb, Alexander Hildebrandt, Eduard Kovalski, Heinrich Lang

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Treatment of Fe(eta(5)-C5H4CH2OH)(2) (1) with two equivalents of ClC(O)R (2) (a, R=2-(C4H3O)-C-c; b, R = 2-(C4H3S)-C-c; c, R = 2-(C4H3S)-C-c); d, R =3-(C4H3S)-C-c) produced the corresponding ferrocenylmethyl carboxylates Fe(eta(5)-C5H4CH2OC(O)R)(2) (3a-d), while the reaction of FcCH(2)OLi (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)) with 2,5-(ClC(O))(2)-(C4H2X)-C-c (5) (a, X = O; b, X = S; c, X = Se) in a 2:1 molar ratio gave 2,5-(FcCH(2)OC(O))(2)-(C4H2X)-C-c (6a-c). Compounds 3a-d and 6a-c were characterized by elemental analysis, NMR (H-1 and C-13{H-1}) and IR spectroscopy. The molecular structures of 3a,b,d in the solid state were determined by single crystal X-ray structure analysis. Compound 3a crystallizes in the monoclinic space group P2(1)/c, while 3b,d crystallize in the triclinic space group P-1. The ester groups and the heteroatoms are in an anti arrangement with respect to each other. Cyclic voltammetry measurements for 3a-d and 6a-c show reversible electrochemical processes (Fc/Fc(+)) between 165 and 176 mV for 3a-d, and 94 and 116 mV for 6a-cb, using [(NBu4)-Bu-n][B(C6F5)(4)] as the supporting electrolyte. It was found that for 3a, a somewhat higher Fc/Fc(+) redox potential (E-0') is observed when compared with the more electron-rich systems 3b,c,d. The molecular electronic structures of the title compounds were additionally investigated by DFT calculations, revealing different degrees of HOMO-LUMO energy gaps within the series, due to a lowering of the LUMO energy, depending on the nature of the heterocyclic ring. (C) 2018 Elsevier Ltd. All rights reserved.

Original languageEnglish
Pages (from-to)188-194
Number of pages7
JournalPolyhedron
Volume152
DOIs
Publication statusPublished - 15 Sep 2018
Externally publishedYes

Cite this

Taher, Deeb ; Ghazzy, Asma ; Awwadi, Firas F. ; Helal, Wissam ; Al Khalyfeh, Khaled ; Korb, Marcus ; Hildebrandt, Alexander ; Kovalski, Eduard ; Lang, Heinrich. / Ferrocenylmethyl-functionalized 5-membered heterocycles : Synthesis, solid-state structure and electrochemical investigations. In: Polyhedron. 2018 ; Vol. 152. pp. 188-194.
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title = "Ferrocenylmethyl-functionalized 5-membered heterocycles: Synthesis, solid-state structure and electrochemical investigations",
abstract = "Treatment of Fe(eta(5)-C5H4CH2OH)(2) (1) with two equivalents of ClC(O)R (2) (a, R=2-(C4H3O)-C-c; b, R = 2-(C4H3S)-C-c; c, R = 2-(C4H3S)-C-c); d, R =3-(C4H3S)-C-c) produced the corresponding ferrocenylmethyl carboxylates Fe(eta(5)-C5H4CH2OC(O)R)(2) (3a-d), while the reaction of FcCH(2)OLi (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)) with 2,5-(ClC(O))(2)-(C4H2X)-C-c (5) (a, X = O; b, X = S; c, X = Se) in a 2:1 molar ratio gave 2,5-(FcCH(2)OC(O))(2)-(C4H2X)-C-c (6a-c). Compounds 3a-d and 6a-c were characterized by elemental analysis, NMR (H-1 and C-13{H-1}) and IR spectroscopy. The molecular structures of 3a,b,d in the solid state were determined by single crystal X-ray structure analysis. Compound 3a crystallizes in the monoclinic space group P2(1)/c, while 3b,d crystallize in the triclinic space group P-1. The ester groups and the heteroatoms are in an anti arrangement with respect to each other. Cyclic voltammetry measurements for 3a-d and 6a-c show reversible electrochemical processes (Fc/Fc(+)) between 165 and 176 mV for 3a-d, and 94 and 116 mV for 6a-cb, using [(NBu4)-Bu-n][B(C6F5)(4)] as the supporting electrolyte. It was found that for 3a, a somewhat higher Fc/Fc(+) redox potential (E-0') is observed when compared with the more electron-rich systems 3b,c,d. The molecular electronic structures of the title compounds were additionally investigated by DFT calculations, revealing different degrees of HOMO-LUMO energy gaps within the series, due to a lowering of the LUMO energy, depending on the nature of the heterocyclic ring. (C) 2018 Elsevier Ltd. All rights reserved.",
keywords = "Ferrocenylmethyl, Heterocycle, Solid state structure, Electrochemistry, DFT calculation, ONE-ELECTRON OXIDATION, CYCLIC VOLTAMMETRY, NONAQUEOUS SOLVENTS, DELTA-E-1/2 VALUES, CHARGE-TRANSFER, COMPLEXES, REACTIVITY, FERROCENE, CHEMISTRY, ACID",
author = "Deeb Taher and Asma Ghazzy and Awwadi, {Firas F.} and Wissam Helal and {Al Khalyfeh}, Khaled and Marcus Korb and Alexander Hildebrandt and Eduard Kovalski and Heinrich Lang",
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Taher, D, Ghazzy, A, Awwadi, FF, Helal, W, Al Khalyfeh, K, Korb, M, Hildebrandt, A, Kovalski, E & Lang, H 2018, 'Ferrocenylmethyl-functionalized 5-membered heterocycles: Synthesis, solid-state structure and electrochemical investigations' Polyhedron, vol. 152, pp. 188-194. https://doi.org/10.1016/j.poly.2018.06.038

Ferrocenylmethyl-functionalized 5-membered heterocycles : Synthesis, solid-state structure and electrochemical investigations. / Taher, Deeb; Ghazzy, Asma; Awwadi, Firas F.; Helal, Wissam; Al Khalyfeh, Khaled; Korb, Marcus; Hildebrandt, Alexander; Kovalski, Eduard; Lang, Heinrich.

In: Polyhedron, Vol. 152, 15.09.2018, p. 188-194.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Ferrocenylmethyl-functionalized 5-membered heterocycles

T2 - Synthesis, solid-state structure and electrochemical investigations

AU - Taher, Deeb

AU - Ghazzy, Asma

AU - Awwadi, Firas F.

AU - Helal, Wissam

AU - Al Khalyfeh, Khaled

AU - Korb, Marcus

AU - Hildebrandt, Alexander

AU - Kovalski, Eduard

AU - Lang, Heinrich

PY - 2018/9/15

Y1 - 2018/9/15

N2 - Treatment of Fe(eta(5)-C5H4CH2OH)(2) (1) with two equivalents of ClC(O)R (2) (a, R=2-(C4H3O)-C-c; b, R = 2-(C4H3S)-C-c; c, R = 2-(C4H3S)-C-c); d, R =3-(C4H3S)-C-c) produced the corresponding ferrocenylmethyl carboxylates Fe(eta(5)-C5H4CH2OC(O)R)(2) (3a-d), while the reaction of FcCH(2)OLi (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)) with 2,5-(ClC(O))(2)-(C4H2X)-C-c (5) (a, X = O; b, X = S; c, X = Se) in a 2:1 molar ratio gave 2,5-(FcCH(2)OC(O))(2)-(C4H2X)-C-c (6a-c). Compounds 3a-d and 6a-c were characterized by elemental analysis, NMR (H-1 and C-13{H-1}) and IR spectroscopy. The molecular structures of 3a,b,d in the solid state were determined by single crystal X-ray structure analysis. Compound 3a crystallizes in the monoclinic space group P2(1)/c, while 3b,d crystallize in the triclinic space group P-1. The ester groups and the heteroatoms are in an anti arrangement with respect to each other. Cyclic voltammetry measurements for 3a-d and 6a-c show reversible electrochemical processes (Fc/Fc(+)) between 165 and 176 mV for 3a-d, and 94 and 116 mV for 6a-cb, using [(NBu4)-Bu-n][B(C6F5)(4)] as the supporting electrolyte. It was found that for 3a, a somewhat higher Fc/Fc(+) redox potential (E-0') is observed when compared with the more electron-rich systems 3b,c,d. The molecular electronic structures of the title compounds were additionally investigated by DFT calculations, revealing different degrees of HOMO-LUMO energy gaps within the series, due to a lowering of the LUMO energy, depending on the nature of the heterocyclic ring. (C) 2018 Elsevier Ltd. All rights reserved.

AB - Treatment of Fe(eta(5)-C5H4CH2OH)(2) (1) with two equivalents of ClC(O)R (2) (a, R=2-(C4H3O)-C-c; b, R = 2-(C4H3S)-C-c; c, R = 2-(C4H3S)-C-c); d, R =3-(C4H3S)-C-c) produced the corresponding ferrocenylmethyl carboxylates Fe(eta(5)-C5H4CH2OC(O)R)(2) (3a-d), while the reaction of FcCH(2)OLi (Fc = Fe(eta(5)-C5H5)(eta(5)-C5H4)) with 2,5-(ClC(O))(2)-(C4H2X)-C-c (5) (a, X = O; b, X = S; c, X = Se) in a 2:1 molar ratio gave 2,5-(FcCH(2)OC(O))(2)-(C4H2X)-C-c (6a-c). Compounds 3a-d and 6a-c were characterized by elemental analysis, NMR (H-1 and C-13{H-1}) and IR spectroscopy. The molecular structures of 3a,b,d in the solid state were determined by single crystal X-ray structure analysis. Compound 3a crystallizes in the monoclinic space group P2(1)/c, while 3b,d crystallize in the triclinic space group P-1. The ester groups and the heteroatoms are in an anti arrangement with respect to each other. Cyclic voltammetry measurements for 3a-d and 6a-c show reversible electrochemical processes (Fc/Fc(+)) between 165 and 176 mV for 3a-d, and 94 and 116 mV for 6a-cb, using [(NBu4)-Bu-n][B(C6F5)(4)] as the supporting electrolyte. It was found that for 3a, a somewhat higher Fc/Fc(+) redox potential (E-0') is observed when compared with the more electron-rich systems 3b,c,d. The molecular electronic structures of the title compounds were additionally investigated by DFT calculations, revealing different degrees of HOMO-LUMO energy gaps within the series, due to a lowering of the LUMO energy, depending on the nature of the heterocyclic ring. (C) 2018 Elsevier Ltd. All rights reserved.

KW - Ferrocenylmethyl

KW - Heterocycle

KW - Solid state structure

KW - Electrochemistry

KW - DFT calculation

KW - ONE-ELECTRON OXIDATION

KW - CYCLIC VOLTAMMETRY

KW - NONAQUEOUS SOLVENTS

KW - DELTA-E-1/2 VALUES

KW - CHARGE-TRANSFER

KW - COMPLEXES

KW - REACTIVITY

KW - FERROCENE

KW - CHEMISTRY

KW - ACID

U2 - 10.1016/j.poly.2018.06.038

DO - 10.1016/j.poly.2018.06.038

M3 - Article

VL - 152

SP - 188

EP - 194

JO - Polyhedron

JF - Polyhedron

SN - 0277-5387

ER -