Ferrocenyl thiocarboxylates: Synthesis, solid-state structure and electrochemical investigations

Deeb Taher, Firas F. Awwadi, J. Matthaeus Speck, Marcus Korb, Christoph Wagner, Emad M. Hamed, Mousa Al-Noaimi, Almeqdad Y. Habashneh, Mohammad El-Khateeb, Sultan T. Abu-Orabi, Kurt Merzweiler, Heinrich Lang

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

The synthesis and characterization of four ferrocenyl thiocarboxylate complexes are reported. Thus, treatment of [Fe(eta(5)-C5H5)(eta(5)-C5H4S-)] (1) with one equivalent of the acid chlorides 2-ClC(O)-(C4H3X)-C-c(2a, X = O; 2b, X = NMe) gave [Fe(eta(5)-C5H5)(eta(5)-C5H4SC(O)-2-(C4H3X)-C-c)] (3a, X = O; 3b, X = NMe (b)). When 1,10-[Fe(eta(5)-C5H4S-)(2)] (4) was reacted with 2-ClC(O)-(C4H3X)-C-c in a 1:2 molar ratio then the respective ferrocenyl-1,1'-bis(thiocarboxylates) 1,10-[Fe(eta(5)-C5H4SC(O)-2-(C4H3X)-C-c)(2)] (5a, X = O; 5b, X = NMe (b)) were produced. The solid state structures of 5a and 5b were determined by X-ray crystal structure analysis. The Crystal structure of 5a indicated the presence of oxygen. oxygen contacts, the inter-oxygen distance is 0.13 angstrom less than the sum of van der Waals radii. Investigation of Cambridge Structural Data base for 2-substtiuted furan molecules indicated the presence of short O. O contacts in 49 examples. Geometrical analysis of the O. O contacts indicated that the geometrical arrangement of these contacts is very similar to the well-defined C-X. X-C contacts (X = Cl, Br or I). Cyclic voltammetric studies of 3a, b and 5a, b showed reversible events at 158 and 243 mV for 3a, b and at 187 and 284 mV for 5a, b, using [(NBu4)-Bu-n][B(C6F5)(4)] as the supporting electrolyte. It was found that the furyl-functionalized systems resulted in a significant higher Fc/Fc(1) redox potential (E-0') as observed for the more electron-rich pyrrolyl derivatives. The Fc/Fc(+) redox potential (E-0') for 5a, b is significantly higher than the one for 3a, b, due to the presence of two electron withdrawing thioester groups attached to the ferrocene in 5a, b. (C) 2017 Elsevier B.V. All rights reserved.

Original languageEnglish
Pages (from-to)59-67
Number of pages9
JournalJournal of Organometallic Chemistry
Volume847
DOIs
Publication statusPublished - 1 Oct 2017
Externally publishedYes

Cite this

Taher, Deeb ; Awwadi, Firas F. ; Speck, J. Matthaeus ; Korb, Marcus ; Wagner, Christoph ; Hamed, Emad M. ; Al-Noaimi, Mousa ; Habashneh, Almeqdad Y. ; El-Khateeb, Mohammad ; Abu-Orabi, Sultan T. ; Merzweiler, Kurt ; Lang, Heinrich. / Ferrocenyl thiocarboxylates : Synthesis, solid-state structure and electrochemical investigations. In: Journal of Organometallic Chemistry. 2017 ; Vol. 847. pp. 59-67.
@article{dc467dc4b1c6459e872fe4ec760d9c23,
title = "Ferrocenyl thiocarboxylates: Synthesis, solid-state structure and electrochemical investigations",
abstract = "The synthesis and characterization of four ferrocenyl thiocarboxylate complexes are reported. Thus, treatment of [Fe(eta(5)-C5H5)(eta(5)-C5H4S-)] (1) with one equivalent of the acid chlorides 2-ClC(O)-(C4H3X)-C-c(2a, X = O; 2b, X = NMe) gave [Fe(eta(5)-C5H5)(eta(5)-C5H4SC(O)-2-(C4H3X)-C-c)] (3a, X = O; 3b, X = NMe (b)). When 1,10-[Fe(eta(5)-C5H4S-)(2)] (4) was reacted with 2-ClC(O)-(C4H3X)-C-c in a 1:2 molar ratio then the respective ferrocenyl-1,1'-bis(thiocarboxylates) 1,10-[Fe(eta(5)-C5H4SC(O)-2-(C4H3X)-C-c)(2)] (5a, X = O; 5b, X = NMe (b)) were produced. The solid state structures of 5a and 5b were determined by X-ray crystal structure analysis. The Crystal structure of 5a indicated the presence of oxygen. oxygen contacts, the inter-oxygen distance is 0.13 angstrom less than the sum of van der Waals radii. Investigation of Cambridge Structural Data base for 2-substtiuted furan molecules indicated the presence of short O. O contacts in 49 examples. Geometrical analysis of the O. O contacts indicated that the geometrical arrangement of these contacts is very similar to the well-defined C-X. X-C contacts (X = Cl, Br or I). Cyclic voltammetric studies of 3a, b and 5a, b showed reversible events at 158 and 243 mV for 3a, b and at 187 and 284 mV for 5a, b, using [(NBu4)-Bu-n][B(C6F5)(4)] as the supporting electrolyte. It was found that the furyl-functionalized systems resulted in a significant higher Fc/Fc(1) redox potential (E-0') as observed for the more electron-rich pyrrolyl derivatives. The Fc/Fc(+) redox potential (E-0') for 5a, b is significantly higher than the one for 3a, b, due to the presence of two electron withdrawing thioester groups attached to the ferrocene in 5a, b. (C) 2017 Elsevier B.V. All rights reserved.",
keywords = "Ferrocene, Sulfur, Furyl, Pyrrolyl, Thiocarboxylates, Chalcogen bond oxygen...oxygen contacts, X-ray structure, Electrochemistry, CYCLIC VOLTAMMETRY, COORDINATION CHEMISTRY, PALLADIUM COMPLEXES, NONAQUEOUS SOLVENTS, DELTA-E-1/2 VALUES, CRYSTAL-STRUCTURE, SULFUR COMPLEXES, IRON COMPLEXES, DERIVATIVES, MOLYBDENUM",
author = "Deeb Taher and Awwadi, {Firas F.} and Speck, {J. Matthaeus} and Marcus Korb and Christoph Wagner and Hamed, {Emad M.} and Mousa Al-Noaimi and Habashneh, {Almeqdad Y.} and Mohammad El-Khateeb and Abu-Orabi, {Sultan T.} and Kurt Merzweiler and Heinrich Lang",
year = "2017",
month = "10",
day = "1",
doi = "10.1016/j.jorganchem.2017.03.053",
language = "English",
volume = "847",
pages = "59--67",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier Science & Technology",

}

Taher, D, Awwadi, FF, Speck, JM, Korb, M, Wagner, C, Hamed, EM, Al-Noaimi, M, Habashneh, AY, El-Khateeb, M, Abu-Orabi, ST, Merzweiler, K & Lang, H 2017, 'Ferrocenyl thiocarboxylates: Synthesis, solid-state structure and electrochemical investigations' Journal of Organometallic Chemistry, vol. 847, pp. 59-67. https://doi.org/10.1016/j.jorganchem.2017.03.053

Ferrocenyl thiocarboxylates : Synthesis, solid-state structure and electrochemical investigations. / Taher, Deeb; Awwadi, Firas F.; Speck, J. Matthaeus; Korb, Marcus; Wagner, Christoph; Hamed, Emad M.; Al-Noaimi, Mousa; Habashneh, Almeqdad Y.; El-Khateeb, Mohammad; Abu-Orabi, Sultan T.; Merzweiler, Kurt; Lang, Heinrich.

In: Journal of Organometallic Chemistry, Vol. 847, 01.10.2017, p. 59-67.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Ferrocenyl thiocarboxylates

T2 - Synthesis, solid-state structure and electrochemical investigations

AU - Taher, Deeb

AU - Awwadi, Firas F.

AU - Speck, J. Matthaeus

AU - Korb, Marcus

AU - Wagner, Christoph

AU - Hamed, Emad M.

AU - Al-Noaimi, Mousa

AU - Habashneh, Almeqdad Y.

AU - El-Khateeb, Mohammad

AU - Abu-Orabi, Sultan T.

AU - Merzweiler, Kurt

AU - Lang, Heinrich

PY - 2017/10/1

Y1 - 2017/10/1

N2 - The synthesis and characterization of four ferrocenyl thiocarboxylate complexes are reported. Thus, treatment of [Fe(eta(5)-C5H5)(eta(5)-C5H4S-)] (1) with one equivalent of the acid chlorides 2-ClC(O)-(C4H3X)-C-c(2a, X = O; 2b, X = NMe) gave [Fe(eta(5)-C5H5)(eta(5)-C5H4SC(O)-2-(C4H3X)-C-c)] (3a, X = O; 3b, X = NMe (b)). When 1,10-[Fe(eta(5)-C5H4S-)(2)] (4) was reacted with 2-ClC(O)-(C4H3X)-C-c in a 1:2 molar ratio then the respective ferrocenyl-1,1'-bis(thiocarboxylates) 1,10-[Fe(eta(5)-C5H4SC(O)-2-(C4H3X)-C-c)(2)] (5a, X = O; 5b, X = NMe (b)) were produced. The solid state structures of 5a and 5b were determined by X-ray crystal structure analysis. The Crystal structure of 5a indicated the presence of oxygen. oxygen contacts, the inter-oxygen distance is 0.13 angstrom less than the sum of van der Waals radii. Investigation of Cambridge Structural Data base for 2-substtiuted furan molecules indicated the presence of short O. O contacts in 49 examples. Geometrical analysis of the O. O contacts indicated that the geometrical arrangement of these contacts is very similar to the well-defined C-X. X-C contacts (X = Cl, Br or I). Cyclic voltammetric studies of 3a, b and 5a, b showed reversible events at 158 and 243 mV for 3a, b and at 187 and 284 mV for 5a, b, using [(NBu4)-Bu-n][B(C6F5)(4)] as the supporting electrolyte. It was found that the furyl-functionalized systems resulted in a significant higher Fc/Fc(1) redox potential (E-0') as observed for the more electron-rich pyrrolyl derivatives. The Fc/Fc(+) redox potential (E-0') for 5a, b is significantly higher than the one for 3a, b, due to the presence of two electron withdrawing thioester groups attached to the ferrocene in 5a, b. (C) 2017 Elsevier B.V. All rights reserved.

AB - The synthesis and characterization of four ferrocenyl thiocarboxylate complexes are reported. Thus, treatment of [Fe(eta(5)-C5H5)(eta(5)-C5H4S-)] (1) with one equivalent of the acid chlorides 2-ClC(O)-(C4H3X)-C-c(2a, X = O; 2b, X = NMe) gave [Fe(eta(5)-C5H5)(eta(5)-C5H4SC(O)-2-(C4H3X)-C-c)] (3a, X = O; 3b, X = NMe (b)). When 1,10-[Fe(eta(5)-C5H4S-)(2)] (4) was reacted with 2-ClC(O)-(C4H3X)-C-c in a 1:2 molar ratio then the respective ferrocenyl-1,1'-bis(thiocarboxylates) 1,10-[Fe(eta(5)-C5H4SC(O)-2-(C4H3X)-C-c)(2)] (5a, X = O; 5b, X = NMe (b)) were produced. The solid state structures of 5a and 5b were determined by X-ray crystal structure analysis. The Crystal structure of 5a indicated the presence of oxygen. oxygen contacts, the inter-oxygen distance is 0.13 angstrom less than the sum of van der Waals radii. Investigation of Cambridge Structural Data base for 2-substtiuted furan molecules indicated the presence of short O. O contacts in 49 examples. Geometrical analysis of the O. O contacts indicated that the geometrical arrangement of these contacts is very similar to the well-defined C-X. X-C contacts (X = Cl, Br or I). Cyclic voltammetric studies of 3a, b and 5a, b showed reversible events at 158 and 243 mV for 3a, b and at 187 and 284 mV for 5a, b, using [(NBu4)-Bu-n][B(C6F5)(4)] as the supporting electrolyte. It was found that the furyl-functionalized systems resulted in a significant higher Fc/Fc(1) redox potential (E-0') as observed for the more electron-rich pyrrolyl derivatives. The Fc/Fc(+) redox potential (E-0') for 5a, b is significantly higher than the one for 3a, b, due to the presence of two electron withdrawing thioester groups attached to the ferrocene in 5a, b. (C) 2017 Elsevier B.V. All rights reserved.

KW - Ferrocene

KW - Sulfur

KW - Furyl

KW - Pyrrolyl

KW - Thiocarboxylates

KW - Chalcogen bond oxygen...oxygen contacts

KW - X-ray structure

KW - Electrochemistry

KW - CYCLIC VOLTAMMETRY

KW - COORDINATION CHEMISTRY

KW - PALLADIUM COMPLEXES

KW - NONAQUEOUS SOLVENTS

KW - DELTA-E-1/2 VALUES

KW - CRYSTAL-STRUCTURE

KW - SULFUR COMPLEXES

KW - IRON COMPLEXES

KW - DERIVATIVES

KW - MOLYBDENUM

U2 - 10.1016/j.jorganchem.2017.03.053

DO - 10.1016/j.jorganchem.2017.03.053

M3 - Article

VL - 847

SP - 59

EP - 67

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -