Issue 23, 2019

Molybdenum(ii) complexes with p-substituted BIAN ligands: synthesis, characterization, biological activity and computational study

Abstract

New complexes [Mo(η3-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 μM 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.

Graphical abstract: Molybdenum(ii) complexes with p-substituted BIAN ligands: synthesis, characterization, biological activity and computational study

Supplementary files

Article information

Article type
Paper
Submitted
31 Ian 2019
Accepted
26 Apr 2019
First published
03 Mai 2019

Dalton Trans., 2019,48, 8449-8463

Molybdenum(II) complexes with p-substituted BIAN ligands: synthesis, characterization, biological activity and computational study

S. Quintal, M. J. Pires da Silva, S. R. M. Martins, R. Sales, V. Félix, M. G. B. Drew, M. Meireles, A. C. Mourato, C. D. Nunes, M. S. Saraiva, M. Machuqueiro and M. J. Calhorda, Dalton Trans., 2019, 48, 8449 DOI: 10.1039/C9DT00469F

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