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Ligand-controlled reactivity and cytotoxicity of cyclometalated rhodium(III) complexes

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Zhang, Wen-Ying, Bridgewater, Hannah E., Banerjee, Samya, Soldevila-Barreda, Joan J., Clarkson, Guy J., Shi, Huayun, Imberti, Cinzia and Sadler, Peter J. (2020) Ligand-controlled reactivity and cytotoxicity of cyclometalated rhodium(III) complexes. European Journal of Inorganic Chemistry, 2020 (11-12). pp. 1052-1060. doi:10.1002/ejic.201901055 ISSN 1434-1948.

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Official URL: http://dx.doi.org/10.1002/ejic.201901055

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Abstract

We report the synthesis, characterization and cytotoxicity of six cyclometalated rhodium(III) complexes [CpXRh(C^N)Z]0/+, in which CpX = Cp*, Cpph, or Cpbiph, C^N = benzo[h]quinoline, and Z = chloride or pyridine. Three X‐ray crystal structures showing the expected “piano‐stool” configurations have been determined. The chlorido complexes hydrolyzed faster in aqueous solution, and reacted preferentially with 9‐ethyl guanine or glutathione compared to their pyridine analogues. The 1‐biphenyl‐2,3,4,5‐tetramethylcyclopentadienyl complex [CpbiphRh(benzo‐[h]quinoline)Cl] (3a) was the most efficient catalyst in coenzyme reduced nicotinamide adenine dinucleotide (NADH) oxidation to NAD+ and induced an elevated level of reactive oxygen species (ROS) in A549 human lung cancer cells. The pyridine complex [CpbiphRh(benzo[h]quinoline)py]+ (3b) was the most potent against A549 lung and A2780 ovarian cancer cell lines, being 5‐fold more active than cisplatin towards A549 cells, and acted as a ROS scavenger. This work highlights a ligand‐controlled strategy to modulate the reactivity and cytotoxicity of cyclometalated rhodium anticancer complexes.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Q Science > QR Microbiology
R Medicine > RC Internal medicine
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH): Antibody-dependent cell cytotoxicity, Rhodium, Antineoplastic agents
Journal or Publication Title: European Journal of Inorganic Chemistry
Publisher: Wiley-VCH Verlag GMBH
ISSN: 1434-1948
Official Date: 27 March 2020
Dates:
DateEvent
27 March 2020Published
20 November 2019Available
20 November 2019Accepted
Volume: 2020
Number: 11-12
Page Range: pp. 1052-1060
DOI: 10.1002/ejic.201901055
Status: Peer Reviewed
Publication Status: Published
Reuse Statement (publisher, data, author rights): This is the peer reviewed version of the following article: Zhang, W. , Bridgewater, H. E., Banerjee, S. , Soldevila‐Barreda, J. J., Clarkson, G. J., Shi, H. , Imberti, C. and Sadler, P. J. (2019), Ligand‐Controlled Reactivity and Cytotoxicity of Cyclometalated Rhodium(III) Complexes. Eur. J. Inorg. Chem.. doi:10.1002/ejic.201901055, which has been published in final form at https://doi.org/10.1002/ejic.201901055. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
Access rights to Published version: Open Access (Creative Commons)
Date of first compliant deposit: 28 November 2019
Date of first compliant Open Access: 20 November 2020
RIOXX Funder/Project Grant:
Project/Grant IDRIOXX Funder NameFunder ID
EP/P030572/1[EPSRC] Engineering and Physical Sciences Research Councilhttp://dx.doi.org/10.13039/501100000266
Chancellor’s International Ph.D. ScholarshipsUniversity of Warwickhttp://dx.doi.org/10.13039/501100000741
NF151429[RS] Royal Societyhttp://dx.doi.org/10.13039/501100000288

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