Al-Riyahee, Ali A. A., Horton, Peter N., Coles, Simon J., Berry, Colin  ORCID: https://orcid.org/0000-0002-9943-548X, Horrocks, Paul D., Pope, Simon J. A. ORCID: https://orcid.org/0000-0001-9110-9711 and Amoroso, Angelo J. ORCID: https://orcid.org/0000-0002-7601-5482
2022.
N,N′-Substituted thioureas and their metal complexes: syntheses, structures and electronic properties.
Dalton Transactions
51
(9)
, pp. 3531-3545.
10.1039/D1DT04091J
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Abstract
The synthesis of six N,N′-substituted thiourea ligands (L1a–L3b) was achieved in two steps. A corresponding extensive series of Cu(I), Cu(II), Ni(II) and Zn(II) complexes (1–24) with varying formulations were synthesised from these ligands by the reaction of a 1 : 1 or a 1 : 2 mixture of Cu(II), Ni(II) and Zn(II) perchlorate or chloride salts. Complexes 1–24 have been comprehensively characterised by mass spectrometry, elemental analysis, UV-vis., IR, and 1H and 13C{1H} NMR spectroscopies where applicable. The X-ray crystal structures were obtained for eight examples: [(L1a)2Cu]ClO4 (1), [(L1c)2Zn](ClO4)2 (4), [(L2a)2Cu]ClO4 (6), [(L2c)2Ni](ClO4)2 (7), [(L1b)2Cu](ClO4) (15), [(L1b)CuCl] (16), [(L4)2CuCl2] (19) and [(L3b)CuClO4] (21). These studies reveal that L1c and L2c represent ligands that have undergone cleavage during reaction with the metal salt; L4 represents an intramolecular rearrangement (via a Hugershoff reaction) of L2b; and in most cases Cu(II) is reduced to Cu(I) during the ligand reaction. The X-ray crystal structures also reveal that 1, 4, 6, 15 and 16 are monometallic species in the solid state; that Cu(I) in 1, 6, 15 and 16 and Zn(II) in 4 are arranged in a distorted tetrahedral geometry; that Cu(I) in 21 adopts a trigonal planar geometry; and that in 7 and 19 the Ni(II) and Cu(II) centres, respectively, possess square planar geometry. Preliminary studies on the biological activity (using the Malaria Sybr Green I Fluorescence assay) of the thiourea containing complexes suggests that the d10 complexes, and increased ligand stoichiometries, may afford higher potency.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry |
| Publisher: | Royal Society of Chemistry |
| ISSN: | 1477-9226 |
| Date of First Compliant Deposit: | 16 March 2022 |
| Date of Acceptance: | 30 January 2022 |
| Last Modified: | 19 Nov 2024 08:45 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/148167 |
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