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
Mixed ligand derivatives of Me2TeLL'2, where L = N,N-dialkyl dithiocarbamate or O,O-alkylene dithiophosphate and L' = O-alkyl dithiocarbonate, have been synthesized and characterized by elemental analysis, 1H, 13C, 31P, and 125Te NMR spectroscopy and infrared and Raman spectroscopy, and X-ray crystallography. Me2Te[S2CNMe2][S2COEt], 8: P[Formula: see text] (no. 2), with cell parameters a = 10.073(3) Å, b = 10.139(2) Å, c = 9.108(2) Å, α = 92.36(2)°, β = 115.55(2)°, γ = 111.19(2)°, V = 760.7(4) Å3, Z = 2, R = 0.0343, Rw = 0.0296. Me2Te[S2CNEt2][S2COMe], 9: P21/c (no. 14) with cell parameters a = 9.881(4) Å, b = 17.671(3) Å, c = 10.149(4) Å, β = 113.65(3)°, V = 1623.3(10) Å3, Z = 4, R = 0.0567, Rw = 0.0514. The immediate environment about tellurium in both molecules is essentially that of a saw-horse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. The S-Te-S angles in the two molecules are 166.87(6)° and 162.0(1)° for 8 and 9, respectively. In both molecules, the TeS bonds to the dithiocarbamate groups are slightly shorter than those to dithiocarbonates. The dithiocarbamate groups are oriented to give secondary interactions involving the apparently terminal sulfur atoms resulting in TeS distances of 3.205(2) and 3.277(4) Å, respectively, in 8 and 9. However, only in 9 is there a similar TeS distance of 3.346(5) Å involving the S2COMe group because in 8, the OEt group of S2COEt, rather than the terminal S atom, is oriented toward Te. Key words: structure, tellurium, methyl, dithiocarbamates, dithiocarbonates, dithiophosphates.