Structures, DNA binding, DNA cleavage, and antitumor investigations of a series of molybdenum(VI) complexes with some N(4) methyl and ethyl thiosemicarbazone ligands

<div><p>Four dioxomolybdenum(VI) complexes were synthesized by reaction of [MoO₂(acac)₂] with thiosemicarbazones derived from 5-allyl-2-hydroxy-3-methoxybenzaldehyde (<b>1</b>), 2-hydroxynaphthaldehyde (<b>2</b>), 2,3-dihydroxybenzaldehyde (<b>3</b>), or 5-tert-butyl-2-hydroxybenzaldehyde (<b>4</b>). The ligands were coordinated to molybdenum as tridentate ONS donors. X-ray crystallography showed that the distorted octahedral coordination of molybdenum is completed by methanol (D) in <b>1a</b>, <b>3a</b>, and <b>4a</b> or H₂O in <b>2a</b>. The molecular structures of <b>1</b>, <b>3</b>, and <b>4</b>, and the complexes were determined by single-crystal X-ray crystallography. Binding of the ligand and complexes with calf thymus DNA were investigated by UV, fluorescence titrations, and viscosity measurements. Gel electrophoresis revealed that all the complexes can cleave pBR322 plasmid DNA. The cytotoxic properties of the complexes against human colorectal (HCT 116) cell line showed strong antiproliferative activities in relative order <b>4a </b>> <b>3a </b>> <b>1a </b>> <b>2a</b> with IC₅₀ values of 1.6, 4.0, 4.8, and 6.7 μM, respectively. The complexes exhibited more activity than the standard reference drug, 5-fluorouracil (IC₅₀ 7.3 μM). These studies show that dioxomolybdenum(VI) complexes have potential use in chemotherapy.</p></div