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Side-bridged cyclam transition metal complexes bearing a phenolic ether or a phenolate pendent arm

Mewis, Ryan E.; Archibald, Stephen J.

Authors

Ryan E. Mewis



Abstract

Side-bridged cyclam transition metal complexes (M = Ni(II), Cu(II) and Zn(II)) bearing a phenolic ether or phenolate pendent arm have been synthesised. For [NiL1]+ and [CuL1]+, evidence for a phenoxyl radical was obtained (quasi reversible peak at +0.74 V and +0.48 V respectively), as well as oxidation of OH, due to protonation of the phenolate, at ∼+1.24 V. The phenoxyl radical in [Ni(L1)]2+ is harder to oxidise by 0.26 V compared with the corresponding Cu(II) complex. UV-Vis data for [Ni(L1)]2+ suggests that the Ni(II) ion may be 4 or 6 coordinate whereas the Cu(II) ion in [Cu(L1)]2+ is five coordinate. The Ni(II) ion in the crystal structure of [Ni(L2)][(ClO4)2] possesses a distorted square-planar geometry in which the phenolic ether pendent arm is not involved in the coordination sphere. The cyclam ligand in this complex adopts a trans-II configuration.

Citation

Mewis, R. E., & Archibald, S. J. (2019). Side-bridged cyclam transition metal complexes bearing a phenolic ether or a phenolate pendent arm. Polyhedron, 171, 578-589. https://doi.org/10.1016/j.poly.2019.08.003

Journal Article Type Article
Acceptance Date Aug 1, 2019
Online Publication Date Aug 10, 2019
Publication Date Oct 1, 2019
Deposit Date Aug 17, 2019
Publicly Available Date Aug 11, 2020
Journal Polyhedron
Print ISSN 0277-5387
Publisher Elsevier
Peer Reviewed Peer Reviewed
Volume 171
Pages 578-589
DOI https://doi.org/10.1016/j.poly.2019.08.003
Keywords Macrocyclic ligands; Azamacrocycles; Cyclam; Bioinorganic; Coordination chemistry
Public URL https://hull-repository.worktribe.com/output/2444111
Publisher URL https://www.sciencedirect.com/science/article/pii/S0277538719305285?via%3Dihub
Additional Information ©2019, Elsevier. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/

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Publisher Licence URL
https://creativecommons.org/licenses/by-nc-nd/4.0/

Copyright Statement
©2019, Elsevier. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/





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