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Synthesis, characterisation and electrochemistry of eight Fe coordination compounds containing substituted 2-(1-(4-R-phenyl-1H-1,2,3-triazol-4-yl)pyridine ligands, R = CH3, OCH3, COOH, F, Cl, CN, H and CF3

Synthesis, characterisation and electrochemistry of eight Fe coordination compounds containing substituted 2-(1-(4-R-phenyl-1H-1,2,3-triazol-4-yl)pyridine ligands, R = CH3, OCH3, COOH, F, Cl, CN, H and CF3
Synthesis, characterisation and electrochemistry of eight Fe coordination compounds containing substituted 2-(1-(4-R-phenyl-1H-1,2,3-triazol-4-yl)pyridine ligands, R = CH3, OCH3, COOH, F, Cl, CN, H and CF3
Eight different Dichloro(bis{2-[1-(4-R-phenyl)-1H-1,2,3-triazol-4-yl-κN3]pyridine-κN})iron(II) compounds, 2–9, have been synthesised and characterised, where group R = CH3 (L2), OCH3 (L3), COOH (L4), F (L5), Cl (L6), CN (L7), H (L8) and CF3 (L9). The single crystal X-ray structure was determined for the L3 which was complemented with Density Functional Theory calculations for all complexes. The structure exhibits a distorted octahedral geometry, with the two triazole ligands coordinated to the iron centre positioned in the equatorial plane and the two chloro atoms in the axial positions. The values of the FeII/III redox couple, observed at ca. −0.3 V versus Fc/Fc+ for complexes 2–9, varied over a very small potential range of 0.05 V. The observation that the different R substituents have virtually no effect on the values of the FeII/III redox couple for all eight complexes 2–9, is explained by the character of the highest molecular orbitals of complexes 2–9, which do not show any communication of electron density between the various ligands and the metal Fe. However, the HOMOs of the free ligands L2 – L9, display extended π-character over the entire ligand, explaining the sensitivity of the 1H NMR C–H-triazole peak, which is dependent on the electron donating/withdrawing power of the R substituent attached to the 2-[1-(4-R-phenyl)-1H-1,2,3-triazol-4-yl]pyridine ligands.
(1,2,3-Triazol-4-yl)pyridine , Redox potential, Iron, DFT
0020-1693
375-385
Conradie, J.
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Conradie, M.M.
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Mtshali, Z.
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van der Westhuizen, D.
c2a09591-31da-43ca-8cc5-785e4a9c125e
Tawfiq, Kinaan M.
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Al-Jeboori, Mohamad J.
180ff82a-635c-452f-925d-c2034b42765b
Coles, S.J.
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Wilson, C.
4dd0bd5c-5d1d-4c2b-b2be-220aa3bf4473
Potgieter, J.H.
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Conradie, J.
814b9b0c-ae44-4f35-b80b-4d27bd575030
Conradie, M.M.
b092ff5b-65d6-4bc6-93f7-2819a613ffaa
Mtshali, Z.
0a1c0336-31f0-4b28-8308-1ca955917fa7
van der Westhuizen, D.
c2a09591-31da-43ca-8cc5-785e4a9c125e
Tawfiq, Kinaan M.
1b5acc5d-c8a9-4113-9637-a8b91717912f
Al-Jeboori, Mohamad J.
180ff82a-635c-452f-925d-c2034b42765b
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Wilson, C.
4dd0bd5c-5d1d-4c2b-b2be-220aa3bf4473
Potgieter, J.H.
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Conradie, J., Conradie, M.M., Mtshali, Z., van der Westhuizen, D., Tawfiq, Kinaan M., Al-Jeboori, Mohamad J., Coles, S.J., Wilson, C. and Potgieter, J.H. (2019) Synthesis, characterisation and electrochemistry of eight Fe coordination compounds containing substituted 2-(1-(4-R-phenyl-1H-1,2,3-triazol-4-yl)pyridine ligands, R = CH3, OCH3, COOH, F, Cl, CN, H and CF3. Inorganica Chimica Acta, 484, 375-385. (doi:10.1016/j.ica.2018.09.056).

Record type: Article

Abstract

Eight different Dichloro(bis{2-[1-(4-R-phenyl)-1H-1,2,3-triazol-4-yl-κN3]pyridine-κN})iron(II) compounds, 2–9, have been synthesised and characterised, where group R = CH3 (L2), OCH3 (L3), COOH (L4), F (L5), Cl (L6), CN (L7), H (L8) and CF3 (L9). The single crystal X-ray structure was determined for the L3 which was complemented with Density Functional Theory calculations for all complexes. The structure exhibits a distorted octahedral geometry, with the two triazole ligands coordinated to the iron centre positioned in the equatorial plane and the two chloro atoms in the axial positions. The values of the FeII/III redox couple, observed at ca. −0.3 V versus Fc/Fc+ for complexes 2–9, varied over a very small potential range of 0.05 V. The observation that the different R substituents have virtually no effect on the values of the FeII/III redox couple for all eight complexes 2–9, is explained by the character of the highest molecular orbitals of complexes 2–9, which do not show any communication of electron density between the various ligands and the metal Fe. However, the HOMOs of the free ligands L2 – L9, display extended π-character over the entire ligand, explaining the sensitivity of the 1H NMR C–H-triazole peak, which is dependent on the electron donating/withdrawing power of the R substituent attached to the 2-[1-(4-R-phenyl)-1H-1,2,3-triazol-4-yl]pyridine ligands.

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Fe-complexes _CV_R1 - Accepted Manuscript
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Accepted/In Press date: 20 September 2018
e-pub ahead of print date: 22 September 2018
Published date: 1 January 2019
Keywords: (1,2,3-Triazol-4-yl)pyridine , Redox potential, Iron, DFT

Identifiers

Local EPrints ID: 427092
URI: https://eprints.soton.ac.uk/id/eprint/427092
ISSN: 0020-1693
PURE UUID: 7ae4a2fa-c774-4f16-b7a3-d1c42ee2c6e4
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 21 Dec 2018 16:31
Last modified: 14 Mar 2019 01:48

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Contributors

Author: J. Conradie
Author: M.M. Conradie
Author: Z. Mtshali
Author: D. van der Westhuizen
Author: Kinaan M. Tawfiq
Author: Mohamad J. Al-Jeboori
Author: S.J. Coles ORCID iD
Author: C. Wilson
Author: J.H. Potgieter

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