Synthesis, spectral and sol-gel behavior of mixed ligand complexes of titanium(IV) with oxygen, nitrogen and sulfur donor ligands

A new route to synthesize nano-sized Ti(IV) mixed ligand complexes have been investigated by the reaction of titanium(IV) chloride with ammonium salts of dithiophosphate and 3(2'-hydroxyphenyl)-5-(4-substituted phenyl) pyrazolines. The resultant complex is then treated with H2S gas to get sulfur bridged dimer of Ti(IV) complex, a precursor of TiS2. The morphology of the complexes was studied by employing XRD which shows that all the complexes are amorphous solid. Molecular weight measurements, elemental analysis in conjugation with spectroscopic (IR, 1H NMR, 13C NMR and 31P NMR) studies revealed the dimeric nature of the complexes in which pyrazoline and dithiophosphate are bidentate. Scanning electron microscopic image and XRD indicate that the particles are in the nano range (50 nm). Putting all the facts together, coordination number six is proposed for titanium with octahedral geometry. KEY WORDS: Titanium(IV), Dithiophosphate, Pyrazoline, Nano-sized, Sol-gel, Mixed ligand complexes Bull. Chem. Soc. Ethiop. 2021, 35(1), 61-76. DOI: https://dx.doi.org/10.4314/bcse.v35i1.5

Biological Applications of Thiocarbohydrazones and Their Metal Complexes: A Perspective Review

Although organic compounds account for more than 99% of currently approved clinical drugs, the established clinical use of cisplatin in cancer or auranofin in rheumatoid arthritis have paved the way to several research initiatives to identify metal-based drugs for a wide range of human diseases. Nitrogen and sulfur donor ligands, characterized by different binding motifs, have been the subject in recent years of one of the main research areas in coordination chemistry. Among the nitrogen/sulfur compounds, very little is known about thiocarbohydrazones (TCH), the higher homologues of the well-known thiosemicarbazones (TSC), and their metal complexes. The extra hydrazine moiety provides the ligands of variable metal binding modes, structural diversity and promising biological implications. The interesting coordination chemistry of TCH has mainly been focused on symmetric derivatives, which are relatively simple to synthesize while few examples of asymmetric ligands have been reported. This informative review on TCHs and their metal complexes will be helpful for improving the design of metal-based pharmaceuticals for applications ranging from anticancer to antinfective therapy.

A polymeric silver thiosaccarinate complex with a two-dimensional triply entangled mesh and argentophilic interactions

Silver(I) complexes with sulfur-donor ligands have a broad range of pharmacological applications. One of the most important factors for tuning the biological activity is the type of donor atom and the ease of ligand replacement. Silver thiosaccharinates display a wide range of structures from mono- to polynuclear complexes. We report the synthesis, crystal structure and vibrational spectroscopic analysis of a two-dimensional AgI–thiosaccharinate coordination polymer, namely poly[tris(μ2-4,4′-bipyridine-κ2N:N′)bis(μ3-1,1-dioxo-1,2-benzisothiazole-3-thiolato-κ3N:S3:S3)bis(μ2-1,1-dioxo-1,2-benzisothiazole-3-thiolato-κ2S3:S3)tetrasilver(I)], [Ag2(C7H4NO2S2)2(C10H8N2)1.5]n, with 4,4′-bipyridine acting as a spacer. A relevant feature of the structure is the presence of an unusually short Ag...Ag separation of 2.8859 (10) Å, well within the range of argentophilic interactions and confirmed as such by Raman analysis of the low-frequency spectrum. From a topological point of view, the structure presents interpenetration in the form of a threefold entangled 2D→2D mesh (2D is two-dimensional).

Electrochemical hydrogenation of a homogeneous nickel complex to form a surface adsorbed hydrogen-evolving species

A Ni(ii) complex with nitrogen and sulfur donor ligands degrades electrochemically in the presence of acid in acetonitrile to form an electrode adsorbed film that catalytically evolves hydrogen.