RESUMEN
The molecular parameters have been calculated to confirm the geometry of 3-methyl-5-oxo-N,1-diphenyl-4,5-dihydro-1-H-pyrazole-4-carbothioamide, HL. The compound is introduced as a new chelating agent for complexation with Cr(III), Fe(III), Co(II), Ni(II) and Cu(II) ions. The isolated chelates were characterized by partial elemental analyses, magnetic moments, spectra (IR, UV-vis, ESR; (1)H NMR) and thermal studies. The protonation constant of HL (5.04) and the stepwise stability constants of its Co(II), Cu(II), Cr(III) and Fe(III) complexes were calculated. The ligand coordinates as a monobasic bidentate through hydroxo and thiol groups in all complexes except Cr(III) which acts as a monobasic monodentate through the enolized carbonyl oxygen. Cr(III) and Fe(III) complexes measured normal magnetic moments; Cu(II) and Co(II) measured subnormal while Ni(II) complex is diamagnetic. The data confirm a high spin and low spin octahedral structures for the Fe(III) and Co(II) complexes. The ESR spectrum of the Cu(II) complex support the binuclear structure. The molecular parameters have also been calculated for the Cu(II) and Fe(III) complexes. The thermal decomposition stages of the complexes confirm the MS to be the residual part. Also, the thermodynamic and kinetic parameters were calculated for some decomposition steps.
Asunto(s)
Metales/química , Compuestos Organometálicos/química , Compuestos Organometálicos/síntesis química , Tioamidas/química , Tioamidas/síntesis química , Espectroscopía de Resonancia por Spin del Electrón , Concentración de Iones de Hidrógeno , Sustancias Macromoleculares/síntesis química , Sustancias Macromoleculares/química , Espectroscopía de Resonancia Magnética , Modelos Biológicos , Modelos Teóricos , Espectrofotometría Infrarroja , TermogravimetríaRESUMEN
Complexes of V(IV)O with N(4) ethyl and/or phenyl thiosemicarbazides have been prepared to study the role of substituents, on the two sides of thiosemicarbazide moiety, on the behavior of the complex formation. The study of ligands in solution reflected the dependence of their ionization values on the nature of the function groups neighboring the active sites. Two main (octahedral and square-pyramid) structures have been characterized for the solid complexes by the well known methods. There is some similarity between the structure and the color of the obtained complexes. Three modes of chelation were suggested for the investigated complexes. Complete disappearance of the nitrile group during the complex formation with cyano ligands is attributed to the promotion of water molecules to the cyano group. The intensity and position of the VO band in the IR spectra reflect not only the nature of the ligand but also the geometry of the complex formed. Some complexes were isolated as binuclear and confirmed by ESR spectra. The end product on thermal degradation of most complexes was VO(2).
Asunto(s)
Tiosemicarbazonas/química , Vanadatos/química , Espectroscopía de Resonancia por Spin del Electrón , Ligandos , Espectrofotometría Infrarroja , Tiosemicarbazonas/metabolismo , Vanadatos/metabolismoRESUMEN
Several complexes of thiosemicarbazone derivatives with Ni(II) have been prepared. Structural investigation of the ligands and their complexes has been made based on elemental analysis, magnetic moment, spectral (UV-Vis, i.r., (1)H NMR, ms), and thermal studies. The i.r. spectra suggest the bidentate mononegative and tridentate (neutral, mono-, and binegative) behavior of the ligands. Different stereochemistries were suggested for the isolated complexes. The thermogravimetry (TG) and derivative thermogravimetry (DTG) have been used to study the thermal decomposition and kinetic parameters of some ligands and complexes using the Coats-Redfern and Horowitz-Metzger equations. The redox properties and stability of the complexes toward oxidation waves explored by cyclic voltammetry are related to the electron withdrawing or releasing ability of the substituent of thiosemicarbazone moiety. The samples displayed Ni(II)/Ni(I) couples irreversible waves associated with Ni(III)/Ni(II) process.