Trimethyltin(IV) Bearing 3-(4-Methyl-2-oxoquinolin-1(2H)-yl)propanoate Causes Lipid Peroxidation-Mediated Autophagic Cell Death in Human Melanoma A375 Cells.

A novel trimethyltin(IV) complex (Me3SnL), derived from 3-(4-methyl-2-oxoquinolin-1(2H)-yl)propanoate ligand, has been synthesized and characterized by elemental microanalysis, UV/Vis spectrophotometry, FT-IR and multinuclear (1H, 13C and 119Sn) NMR spectroscopies. Furthermore, the structure of the ligand precursor HL was solved using SC-XRD (single-crystal X-ray diffraction). The prediction of UV/Vis and NMR spectra by quantum-chemical methods was performed and compared to experimental findings. The protein binding affinity of Me3SnL towards BSA was determined by spectrofluorometric titration and subsequent molecular docking simulations. Me3SnL has been evaluated for its in vitro anticancer activity against three human cell lines, MCF-7 (breast adenocarcinoma), A375 (melanoma) and HCT116 (colorectal carcinoma), and three mouse tumor cell lines, 4T1 (breast carcinoma), B16 (melanoma) and CT26 (colon carcinoma), using MTT and CV assays. The strong inhibition of A375 cell proliferation, ROS/RNS upregulation and robust lipid peroxidation lead to autophagic cell death upon treatment with Me3SnL.

A Planar Five-Membered Aromatic Ring Stabilized by Only Two π-Electrons.

Many chemicals known today are partially or fully aromatic, since a ring framework experiences additional stabilization through the delocalization of π-electrons. While aromatic rings with equal numbers of π-electrons and ring atoms such as benzene are particularly stable, those with the minimally required two π-electrons are very rare and yet remain limited to three- and four-membered rings if not stabilized in the coordination sphere of heavy metals. Here we report the facile synthesis of a dipotassium cyclopentagallene, a unique example of a five-membered aromatic ring stabilized by only two π-electrons. Single-crystal X-ray diffraction revealed a planar Ga5 ring with almost equal gallium-gallium bond lengths, which together with computational and spectroscopic data confirm its aromatic character. Our results prove that aromatic stabilization goes far beyond what has previously been assumed as minimum π-electron count in a five-atom ring fragment.

Ditopic bis(N,N',N'-substituted 1,2-ethanediamine) ligands: synthesis and coordination chemistry.

The synthesis of two different types of bis(N,N',N'-substituted 1,2-ethanediamine)s, bridged either through the secondary (type 1) or tertiary (type 2) amine groups is reported. Selected protio-ligands have been applied in subsequent metallation reactions using aluminium, magnesium, tin, and zinc sources allowing to isolate five mononuclear and eight dinuclear complexes. All complexes have been fully characterized and their solid-state structures have been studied by means of single-crystal X-ray diffraction analysis. Nine of the 13 complexes carry reactive alkyl, amide or hydride groups, which indicates their potential as catalysts or supports for (transition) metals.

Magnesium bis(amidinate) and bis(guanidinate) complexes: impact of the ligand backbone and bridging groups on the coordination behaviour.

A library of ten dinucleating bis(amidine) and bis(guanidine) ligands, in which the bridging groups, terminal rests, and backbone substituents were systematically altered, has been synthesized and subsequently applied in metallation reactions using three different magnesium sources. Eight Mg complexes could be isolated and fully characterized, and in seven cases their solid-state structure could be determined by means of single crystal X-ray diffraction analysis. The results evidence a versatile coordination behaviour, which ranges from the first dinuclear heteroleptic magnesium iodide complex to dinuclear homoleptic complexes. These findings indicate the crucial impact of both the ligand and the magnesium source not only on the accessibility of well-defined dinuclear complexes but also on the aggregation in solution and in the solid state.