Four novel dimeric bis-μ-imido bridged metal-metal bonded oxidomolybdenum(V) complexes [MoV2O2Lâ²21-4] (1-4) (where Lâ²1-4are rearranged ligands formed in situ from H2L1-4) and a new mononuclear dioxidomolybdenum(VI) complex [MoVIO2L5] (5) synthesized from salen type N2O2ligands are reported. This rare series of imido-bridged complexes (1-4) have been furnished from rearranged H3Lâ²1-4ligands, containing an aromatic diimine (o-phenylenediamine) "linker", where Mo assisted hydrolysis followed by -C=N bond cleavage of one of the arms of the ligand H2L1-4took place. A monomeric molybdenum(V) intermediate species [MoVO(HLâ²1-4)(OEt)] (Id1-4) was generated in situ. The concomitant deprotonation and dimerization of two molybdenum(V) intermediate species (Id1-4) ultimately resulted in the formation of a bis-μ-imido bridge between the two molybdenum centers of [MoV2O2Lâ²21-4] (1-4). The mechanism of formation of 1-4 has been discussed, and one of the rare intermediate monomeric molybdenum(V) species Id4has been isolated in the solid state and characterized. The monomeric dioxidomolybdenum(VI) complex [MoVIO2L5] (5) was prepared from the ligand H2L5where the aromatic "linker" was replaced by an aliphatic diimine (1,2-diaminopropane). All the ligands and complexes have been characterized by elemental analysis, IR, UV-vis spectroscopy, NMR, ESI-MS, and cyclic voltammetry, and the structural features of 1, 2, 4, and 5 have been solved by X-ray crystallography. The DNA binding and cleavage activity of 1-5 have been explored. The complexes interact with CT-DNA by the groove binding mode, and the binding constants range between 103and 104M-1. Fairly good photoinduced cleavage of pUC19 supercoiled plasmid DNA was exhibited by all the complexes, with 4 showing the most promising photoinduced DNA cleavage activity of â¼93%. Moreover, in vitro cytotoxic activity of all the complexes was evaluated by MTT assay, which reveals that the complexes induce cell death in MCF-7 (human breast adenocarcinoma) and HCT-15 (colon cancer) cell lines.
Monomeric and Dimeric Oxidomolybdenum(V and VI) Complexes, Cytotoxicity, and DNA Interaction Studies: Molybdenum Assisted C=N Bond Cleavage of Salophen Ligands / Majumder, Sudarshana; Pasayat, Sagarika; Panda, Alok K.; Dash, Subhashree P.; Roy, Satabdi; Biswas, Ashis; Varma, Mokshada E.; Joshi, Bimba N.; Garribba, Eugenio; Kausar, Chahat; Patra, Samir Kumar; Kaminsky, Werner; Crochet, Aurã©lien; Dinda, Rupam. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 56:18(2017), pp. 11190-11210. [10.1021/acs.inorgchem.7b01578]
Monomeric and Dimeric Oxidomolybdenum(V and VI) Complexes, Cytotoxicity, and DNA Interaction Studies: Molybdenum Assisted C=N Bond Cleavage of Salophen Ligands
GARRIBBA, Eugenio;
2017-01-01
Abstract
Four novel dimeric bis-μ-imido bridged metal-metal bonded oxidomolybdenum(V) complexes [MoV2O2Lâ²21-4] (1-4) (where Lâ²1-4are rearranged ligands formed in situ from H2L1-4) and a new mononuclear dioxidomolybdenum(VI) complex [MoVIO2L5] (5) synthesized from salen type N2O2ligands are reported. This rare series of imido-bridged complexes (1-4) have been furnished from rearranged H3Lâ²1-4ligands, containing an aromatic diimine (o-phenylenediamine) "linker", where Mo assisted hydrolysis followed by -C=N bond cleavage of one of the arms of the ligand H2L1-4took place. A monomeric molybdenum(V) intermediate species [MoVO(HLâ²1-4)(OEt)] (Id1-4) was generated in situ. The concomitant deprotonation and dimerization of two molybdenum(V) intermediate species (Id1-4) ultimately resulted in the formation of a bis-μ-imido bridge between the two molybdenum centers of [MoV2O2Lâ²21-4] (1-4). The mechanism of formation of 1-4 has been discussed, and one of the rare intermediate monomeric molybdenum(V) species Id4has been isolated in the solid state and characterized. The monomeric dioxidomolybdenum(VI) complex [MoVIO2L5] (5) was prepared from the ligand H2L5where the aromatic "linker" was replaced by an aliphatic diimine (1,2-diaminopropane). All the ligands and complexes have been characterized by elemental analysis, IR, UV-vis spectroscopy, NMR, ESI-MS, and cyclic voltammetry, and the structural features of 1, 2, 4, and 5 have been solved by X-ray crystallography. The DNA binding and cleavage activity of 1-5 have been explored. The complexes interact with CT-DNA by the groove binding mode, and the binding constants range between 103and 104M-1. Fairly good photoinduced cleavage of pUC19 supercoiled plasmid DNA was exhibited by all the complexes, with 4 showing the most promising photoinduced DNA cleavage activity of â¼93%. Moreover, in vitro cytotoxic activity of all the complexes was evaluated by MTT assay, which reveals that the complexes induce cell death in MCF-7 (human breast adenocarcinoma) and HCT-15 (colon cancer) cell lines.File | Dimensione | Formato | |
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