Genda Singh
Banaras Hindu University
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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy | 1991
Genda Singh; T.R. Rao
Abstract Salicylaldehyde(N-benzoyl)glycyl hydrazone (SalBzGH) has been synthesized and characterized. Metal complexes of the empirical formula [Ln(SalBzGH-2H)OH(H2O)2] where Ln = Y, Pr, Nd, Sm, Eu, Gd and Dy, have been synthesized and their structures studied by infrared, far-infrared, absorption, emission and NMR spectra. 1H and 13C NMR spectra indicate the presence of dynamic equilibrium between two isomers of SalBzGH over the 298–368 K temperature range and stabilization of a single isomer upon complexation with Ln(III). The hypersensitive band profile of the Nd(III) complex indicates a change in metal coordination number due to solvation, while an increase of temperature results in a decrease of emax of the hypersensitive band. The emission spectrum of [Eu(SalBzGH-2H)OH(H2O)2] at 77 K indicates a low site symmetry. SalBzGH coordinates through imidolic oxygen, azomethine nitrogen and phenolate oxygen.
Transition Metal Chemistry | 1989
T.R. Rao; Genda Singh; Israr A. Khan
SummaryN-benzoylglycine hydrazide (BzGH) reacts with trivalent lanthanide metal ions forming complexes of the type [Ln(BzGH)2Cl(H2O)2]Cl2·nH2O, where Ln=LaIII, PrIII, NdIII, SmIII, EuIII, GdIII, TbIII, DyIII, or YIII;n=1 or 2. The structures of the complexes have been studied by conductance, magnetic, electronic, i.r.,1H n.m.r. and13C n.m.r. spectral techniques. The nephelauxetic ratio, the bonding parameter, Sinhas parameter and the covalency angular overlap parameter have been calculated from the electronic spectra of PrIII, NdIII and SmIII complexes. Seven-coordination is proposed in the NdIII complex. The i.r. and1H n.m.r. spectral data suggest bidentate BzGH in all the complexes.
Transition Metal Chemistry | 1989
T.R. Rao; Genda Singh
Summaryo-Hydroxyacetophenone (N-benzoyl)glycyl hydrazone (o-HABzGH) has been characterized by i.r.,1H n.m.r.,13C n.m.r. and mass spectral studies, and its complexes of the types [Ln(o-HABzGH)Cl2(H2O)2]Cl and [Ln(o-HABzGH−2H)OH(H2O)3], where Ln=La, Pr, Nd, Sm and Eu, have been synthesized. The structures of the complexes have been studied by conductance, magnetic, electronic, i.r.,1H n.m.r. and13C n.m.r. spectral techniques. The hypersensitive bands of the electronic spectra suggest coordination numbers six and seven around NdIII in its adduct and neutral complexes respectively. I.r. and n.m.r. spectral data suggest a neutral bidentate behaviour for the ligand in the adducts and a dinegative tridentate nature in the neutral complexes.
Synthesis and Reactivity in Inorganic and Metal-organic Chemistry | 1990
T.R. Rao; Genda Singh
Abstract 2-Acetylpyridineisonicotinoylhydrazone (2-ApINH) upon reaction with 4f metal ions, gave complexes of the formulae [M(2-ApINH)2Cl2]Cl and [M(2-ApINH-H)2OH] [M = Y(III), Gd(III), Tb(III) and Dy(III)]. The structures of the complexes have been studied by elemental analysis, molar conductance, magnetic susceptibility, electronic, IR, 1H and 13C NMR spectral techniques. The bonding parameters, viz., β, b1/2, δ(%) and χ have been calculated from the absorption spectra of the Dy(III) complexes. IR and NMR spectral data suggest non-deprotonated tridentate 2-ApINH in the eight-coordinated addition complexes and uninegative tridentate 2-ApINH in the seven-coordinated, neutral complexes.
Synthesis and Reactivity in Inorganic and Metal-organic Chemistry | 1989
T.R. Rao; Genda Singh
Abstract Acetone (N-benzoyl)glycyl hydrazone (BzAGH) has been found to react with trivalent lanthanide metal ions to form complexes of the type [Ln(BzAGH)Cl(H2O)3]Cl2 where Ln = La(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III) and Dy(III). The complexes have been characterized by elemental analyses, molar conductance, magnetic, electronic, IR, 1H NMR and 13C NMR spectral techniques. Molar conductance studies in 0.001 M MeOH solutions indicate a 2:1 electrolytic behaviour of all the complexes. The nephelauxetic ratio, the bonding parameter, the Sinhas parameter and the covalency angular overlap parameter have been calculated from the electronic spectra of the Pr(III), Nd(III) and Sm(III) complexes. The IR and 1H NMR spectral studies reveal that BzAGH acts as a neutral bidentate chelating ligand in the complexes.
Synthesis and Reactivity in Inorganic and Metal-organic Chemistry | 1992
T. R. Rao; Madhu Srivastava; Genda Singh
Abstract Trivalent lanthanide complexes of nicotinic acid hydrazide (NicHz) of the type Ln(NicHz)3Cl3.n EtOH [Ln = La, Pr, Nd, Sm for n = 2; Ln = Eu, Gd, Tb, Dy and Y for n = l] have been synthesised. The hypersensitive band profile of the electronic spectrum indicates an eight-coordination around neodymium and the molar absorptivity has been found to increase with increasing pH and to decrease with increasing temperature (30–80°C). FT-far IR spectra indicate a transconfiguration of the two chloro groups within the coordination sphere. A square antiprismatic structure has been proposed for the complexes.
Synthesis and Reactivity in Inorganic and Metal-organic Chemistry | 1991
T. R. Rao; Genda Singh
Abstract Furfural isonicotinoylhydrazone (FINH)has been synthesised, characterized by IR, 1H and 13C NMR and mass spectral studies, and its complexes of the type [Ln(FINH)2 Cl3], where Ln=La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III) and Y(III), have been synthesized and subjected to elemental analysis, molar conductance, magnetic susceptibility, electronic, infrared, 1H and 13C NMR spectral tectniques. The parameters, β b½, 3(%) and η calculated from the absorption spectra of Nd(III) and Pr(III) complexes suggest a weak covalent bond formation between these metal ions and the ligand. Infrared and NMR spectral data suggest, a neutral bidentate nature of FINH in the complexes. The absorption spectral profile suggests a seven-coordination number around the Nd(III) ion in the complex.
Journal of Chemical Sciences | 1991
Genda Singh; Madhu Srivastava; Pariti S S J Sastry; T. R. Rao
Some trivalent lanthanide complexes of acetone isonicotinoylhydrazone (AINH), having the empirical formula Ln(AINH)3Cl3, where Ln=La(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Tb(III), Dy(III) and Y(III) were prepared. Elemental analyses, molar conductance, magnetic susceptibility, IR, electronic,1H,13C and139La NMR spectra of the complexes have been examined. It has been found that AINH behaves as a neutral bidentate ligand coordinating through the carbonyl oxygen and azomethine nitrogen. Temperature-dependence of the molar absorptivity and the metal coordination number has been established by the electronic spectra of Nd(AINH)3Cl3 recorded over the 28–80°C range.
Journal of Chemical Sciences | 1989
T.R. Rao; Genda Singh
Abstracto-Hydroxyacetophenone (N-benzoyl)glycyl hydrazone (o-HABzGH) forms complexes of the types [M(o-HABzGH)Cl2(H2O)2]Cl and [M(o-HABzGH-2H)OH(H2O)2], where M = Y(III), Gd(III), Tb(III) and Dy(III). The complexes have been characterized by elemental analyses, molar conductance, magnetic susceptibility, infrared, electronic,1H NMR and13C NMR spectral techniques. The nephelauxetic ratio (β), covalency (δ), bonding parameter (b1/2) and angular overlap parameter (η) have been calculated from Dy(III) complexes. Infrared and NMR spectral studies show thato-HABzGH acts as a neutral bidentate ligand in the adduct complexes and as a dinegative tridentate one in the neutral complexes. A coordination number of six has been proposed for the metal ion in all the complexes.
Crystal Research and Technology | 1989
T.R. Rao; Genda Singh