Molybdenum(ii) complexes with p-substituted BIAN ligands: synthesis, characterization, biological activity and computational study
authors Quintal, S; da Silva, MJP; Martins, SRM; Sales, R; Felix, V; Drew, MGB; Meireles, M; Mourato, AC; Nunes, CD; Saraiva, MS; Machuqueiro, M; Calhorda, MJ
nationality International
journal DALTON TRANSACTIONS
keywords DICARBONYL COMPLEXES; DYNAMIC-BEHAVIOR; DIIMINE; CATALYSTS; DNA; POLYMERIZATION; CYTOTOXICITY; MONONUCLEAR; EQUILIBRIA; REACTIVITY
abstract New complexes [Mo(eta(3)-C3H5)X(CO)(2)(4-Y-BIAN)] (4-Y-BIAN = bis(4-Y-phenyl)-acenaphthenequinonediimine), with X = Br and Y = H, Me, OMe, COOH and X = Cl, Y = OMe, as well as the cation with X = NCMe and Y = OMe were synthesized, expanding the scope of this family. Two single crystal X-ray structures (X = Br, Y = Me, OMe) display a less symmetric arrangement (axial isomer), where one N donor atom is trans to the allyl group and the second to one CO. DFT studies showed similar energies for the two possible isomers of the complexes, with a very small preference for the observed axial isomer. The HOMO of the complexes is localized in the metal and the HOMO-1 of the oxidized species has a contribution from the BIAN ligand, while the LUMO is fully localized in BIAN. Electrochemical studies showed one process corresponding to the oxidation of Mo(ii) to Mo(iii) for complexes with X = Br, Y = H, Me, and two oxidation reactions for those with X = Br, Y = Cl, OMe, while the COOH derivative exhibited no oxidation wave. The antitumor effect of the complexes with X = Br was tested in cancer lines, and the H and OMe complexes were particularly active, with EC50 values below 8 mu M in HeLa cell lines. The DNA binding constants determined by titration experiments were comparable with those of doxorubicin and ethidium bromide, suggesting a mechanism of action based on intercalation in DNA.
publisher ROYAL SOC CHEMISTRY
issn 1477-9226
isbn 1477-9234
year published 2019
volume 48
issue 23
beginning page 8449
ending page 8463
digital object identifier (doi) 10.1039/c9dt00469f
web of science category Chemistry, Inorganic & Nuclear
subject category Chemistry
unique article identifier WOS:000472537600047
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journal impact factor 4.174
5 year journal impact factor 3.812
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