The vibrational analysis of some oxamide complexes

Summary The vibrational spectra of the oxamide and deuteriooxamide complexes with Ni^II, Pd^II, Cu^II, Zn^II and Co^III are presented. The vibrational analysis is given for a planarD _2h structure for the Ni^II, Cu^II and Pd^II compounds; the Zn^II and Co^III complexes have a tetrahedral and octahedral structure respectively.Presented in part at the XIX I.C.C.C. Prague 1978.     

Kinetics of the mediatory reduction ofgem-dichlorocyclopropanes

The effect of the nature of organic electron transfer agents and of Pt^II, Pd^II, Rh^II, Co^II, Ni^II, Cu^II, Cr^III, Mn^II, Ti^III, V^III, Zn^II, and Ag^I metal ions on the kinetics of the homogeneous reduction ofgem-dichlorocyclopropanes has been studied. Pt^II, Pd^II, Rh^III, Co^II, and Ni^II ions accelerate this process, V^III and Ag^I ions exert practically no effect on the reduction rate, and the rest of the metal ions exhibit inhibitor properties.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1407–1410, August, 1993.     

Chelatbildung mit 1,3-Diamino-2-methylenpropanen

Chelate Formation with 1,3-Diamino-2-methylene Propane1 1,3-Diamino-2-methylene propane and its N, N′ alkylated derivatives form crystalline chelates with Co^II (1:3), Ni^II (1:1, 1:2 and 1:3), Pd^II (1:1, 1:2), Rh^III (1:1) and Cu^II (1:2). Experiments for preparation of olefin complexes were unsuccessful. By potentiometric measurements the base strengths of the ligands as well as the stability constants of the Co^II, Ni^II, Pd^II, Cu^II, Zn^II, Cd^II chelates were evaluated and the kinetics of the formation of the 1:1 Pd^II complex is investigated. The magnetic behaviour of the Co^II?, Pd^II? and Cu^II? chelates is normal, whereas[Ni(dia)₂(H₂O)₂] (ClO₄)₂ shows anormal behaviour due to configurational isomerism between square planar and octahedral ligand geometry in solid state in type of a LIFSCHITZ -isomerism. The ESR-spectra of the Cu^II?compounds are discussed and the bonding parameters of the Cu? N?bonds were calculated.     

Complexes of 1-isonicotinoyl-4-benzoyl-3-thiosemicarbazide with manganese(II), iron(III), chromium(III), cobalt(II), nickel(II), copper(II) and zinc(II)

1-Isonicotinoyl-4-benzoyl-3-thiosemicarbazide (IBtsc) and its Cr^III, Mn^II, Fe^III, Co^II, Ni^II, Cu^II and Zn^II complexes have been prepared and characterized by elemental analyses, magnetic susceptibility measurements, u.v.–vis., i.r., n.m.r. and FAB mass spectral data. The room temperature e.s.r. spectra of the Cr^III, Fe^III and Cu^II complexes yield values, characteristic of octahedral, tetrahedral and square-planar complexes, respectively. The Mössbauer spectra of [Fe(IBtsc-H)Cl₂] at room temperature and at 78 K suggest the presence of high-spin Fe^III. The Ni^II, Cr^III and Cu^II complexes show semiconducting behaviour in the solid state, but the Zn^II complex is an insulator at room temperature. IBtsc and its soluble complexes have been screened against several bacteria, fungi and tumour cell lines.     

Ligational behaviour of biacetylmonoxime nicotinoyl hydrazone (H2BMNH) towards transition metal ions

Summary The synthesis and characterization of Mn^II, Co^II, Ni^II, Cu^II, Zn^II, Cd^II UO ₂ ²⁺ , Cr^III and Fe^III complexes of biacetylmonoxime nicotinoyl hydrazone (H₂BMNH) are reported. Elemental analysis, molar conductance, magnetic moment and spectral (i.r., visible and n.m.r.) measurements have been used to characterize the complexes. I.r. spectral data show that the ligand behaves in a bidentate and/or tridentate manner. An octahedral structure is proposed for the Mn^II, Ni^II, Cr^III and Fe^III complexes, while a square-planar structure is proposed for both Co^II and Cu^II complexes on the basis of magnetic and spectral measurements.     

Ligational behaviour of a tetradentate NONS donor ligand towards some transition metal ions

Summary The synthesis and characterization of Cr^II, Mn^II, Fe^II, Co^II, Ni^II, Pd^II, Cu^II, Zn^II, Cd^II and UO ₂ ²⁺ complexes of 1-meotinoyl-4-phenyl-3-thiosemicarbazide (H₂NTS) are reported. I.r. spectral data show that the ligand behaves in a bidentate and/or tetradentate manner. An octahedral structure is proposed for the Cr^II, Fe^II and Ni^II complexes; a tetrahedral structure for the Mn^II, Co^II and Cu(NTS)·2H₂O complexes; and a square planar structure for the Pd^II and Cu(HNTS)Cl·H₂O complexes. The i.r. data suggest that the Fe^II complex contains a hydroxo bridge.     

1, 3, 4-Thiadiazole-2, 5-dithiol as a Complexing Agent II. Complexes of NiII,RhI, PdII,PtII, AuIII,and CuII

1, 3, 4-Thiadiazol-2, 5-Dithiol als Komplexierungsreagenz. II. Komplexe des Ni^II, Rh^I, Pd^II, Pt^II, Au^III und Cu^II Complexes of Ni^II, Rh^I, Pd^II, Pt^II, Au^III, and Cu^II with 1, 3, 4-thiadiazole-2, 5- dithiol have been prepared. Probable structures have been proposed for the complexes on the basis of chemical analysis, magnetic susceptibility and spectral data. Crystal field parameters have been calculated which are in keeping with the structures proposed.     

Transition metal complexes derived from N-isonicotinamido-N′-benzoylthiocarbamide (H2IBTC)

Summary The synthesis and characterization of Cr^III, Mn^II, Fe^III, Co^II, Ni^II, Cu^II, Zn^II, Cd^II and UO _inf2 ^sup2+ complexes of N-isonicotinamido-_N-benzoylthiocarbamide (H₂IBTC) are reported. I.r. spectral data show that the ligand behaves in a bidentate, tridentate and/or tetradentate manner. Different stereochemistries are proposed for Cr^III, Mn^II, Fe^III, Co^II, Ni^II and Cu^II complexes on the basis of spectral and magnetic studies. The i.r. data indicate that the carbonyl oxygen of the benzoyl moiety is the backbone of chelation in most complexes.     

New complexes of iron(III), cobalt(II), nickel(II) and copper(II) with 2-phenyl-1,2,3-triazole-4-carboxalidene-2-aminophenol

Summary Fe^III, Co^II, Ni^II and Cu^II complexes of a new Schiff base, 2-phenyl-1,2,3-triazole-4-carboxalidene-2-aminophenol (PTCAP), have been synthesized and characterized by elemental analyses, molar conductance and magnetic susceptibility measurements, and by u.v.-vis., i.r. and e.p.r. spectral observations. The studies indicate an octahedral structure for the complexes with the general formula [ML₂] (M = Co^II, Ni^II or Cu^II.; L = PTCAP) or [M′(OH)L₂] (M′ = Fe^III). The i.r. spectra suggest that the ligand acts as a tridentate (NNO) donor towards Co^II, Ni^II and Cu^II, and, in the Fe^III complex, one of the two ligand molecules acts as a bidentate (NO) donor and the other as a tridentate donor. The M?ssbauer spectrum of the Fe^III complex suggests the presence of a spin equilibrium at room temperature. Cyclic voltammograms are also recorded for the Cu^II and Fe^III complexes.     

Copper,nickel and cobalt complexes of Schiff-bases derived from β-diketones

Complexes of Cu^II, Ni^II, Co^II and Fe^III with Schiff-bases derived by condensing o-aminophenol and ethanolamine with dibenzoylmethane, benzoylacetone, acetylacetone and thenoyltrifluoroacetone have been prepared and characterized by elemental analysis, electrical conductivity, magnetic moment, d.t.a. and t.g.a. measurements, i.r., u.v.–vis., e.s.r. and Mössbauer spectra. All the complexes are non-electrolytes. Those with 1:2 metal:ligand ratios have an octahedral or distorted octahedral environment. Square-planar, T_d or D_2d structures have been proposed for the 1:1 complexes. The Mössbauer spectrum of the Fe^III complex confirms its high-spin octahedral stereochemistry.     

Chelated complexes of cadmium(II), cobalt(II), copper(II), mercury(II), nickel(II), uranyl(II) and zinc(II) with benzil bis(4-phenylthiosemicarbazone)

Summary Complexes of Co^II, Ni^II, Cu^II, Zn^II, Cd^II, Hg^II and UO ₂ ^II with benzil bis(4-phenylthiosemicarbazone), H₂BPT, have been synthesized and their structures assigned based on elemental analysis, molar conductivity, magnetic susceptibility and spectroscopic measurements. The i.r. spectra suggest that the ligand behaves as a binegative quadridentate (NSSN) (Co^II, Cu^II, Hg^II and UO ₂ ^II complexes) or as a binegative quadridentate-neutral bidentate chelating agent (Ni^II, Zn^II and Cd^II complexes). Octahedral structures for the Co^II and Ni^II complexes and square-planar structure for the Cu^II complex are suggested on the basis of magnetic and spectral evidence. The crystal field parameters (Dq, B and _B) for the Co^II complex are calculated and agree fairly well with the values reported for known octahedral complexes. The ligand can be used for the microdetermination of Ni^II ions of concentration in the 0.4–6×10^–4 mol l^–1 range and the apparent formation constant for the species generated in solution has also been calculated.     

Transition metal complexes derived from ethyl-α-(N-phenylthiocarbamyl)cyanoacetate

Summary Complexes of Co^II, Ni^II, Cu^II, Zn^II, Pd^II, Cd^II, Hg^II and Cu^I with ethyl--(N-phenylthiocarbamyl)cyanoacetate (HETCA) have been synthesized and characterized. The i.r. spectra show that HETCA behaves as a mononegative bidentate ligand, in the thiol tautomeric form. HETCA reduces CuCl₂ to give a diamagnetic Cu^I complex. A tetrahedral structure is proposed for the Co^II complex, while a square-planar structure is proposed for the Ni^II, Cu^II, and Pd^II complexes.     

Chromium(III), manganese(II), cobalt(II), nickel(II), copper(II) and palladium(II) complexes of a 12-membered tetraaza [N4] macrocyclic ligand

Cr^III, Mn^II, Co^II, Ni^II, Cu^II and Pd^II complexes of the macrocyclic ligand, 2,3,5,8,9,11 hexamethyl-1,4,7,10 tetraaza- cyclododeca-1,3,7,9 tetraene (DADAP), have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibility measurements, i.r., electronic and e.p.r. spectral studies. These spectral studies suggest an octahedral geometry for the Cr^III, Mn^II and Co^II, square planar geometry for Ni^II and Pd^II and tetragonal geometry for Cu^II complexes.     

Darstellung und Charakterisierung einige Thiocyanat- und Selenocyanat-Komplexe von Übergangsmetallen

Some 6:1 thiocyanate complexes of Fe^III, Mo^III, Ru^III, Os^III, Ir^III and some 6:1 or 4:1 selenocyanate complexes of Fe^II, Fe^III, Mo^III, Rh^III, Pd^II, Pt^II, and Au^III have been prepared as salts of large organic cations. The compounds are characterized by their infra-red spectra and by conductance measurements. In particular the linkage property of the thiocyanate and selenocyanate ligand is discussed together with the consequences it has on the AHRLAND -CHATT -DAVIES -PEARSON classification of the central ions.     

The synthesis,characterization and spectral studies of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes with N,N-bis(2-{[(2-methyl-2-phenyl-1,3-dioxolan-4-yl) methyl]amino}butyl) N′,N′-dihydroxyethanediimidamide

Co^II, Ni^II, Cu^II, Zn^II and Cd^II complexes of N,N-bis(2-{[(2-methyl-2-phenyl-1,3-dioxolan-4-yl)methyl]amino}butyl)N′,N′-dihydroxyethanediimidamide (LH₂) were synthesized and characterized by elemental analyses, IR, ¹H- and ¹³C-NMR spectra, electronic spectra, magnetic susceptibility measurements, conductivity measurements and thermogravimetric analyses (TGA). The Co^II, Ni^II and Cu^II complexes of LH₂ were synthesized with 1?:?2 metal ligand stoichiometry. Zn^II and Cd^II complexes with LH₂ have a metal ligand ratio of 1?:?1. The reaction of LH₂ with Co^II, Ni^II, Cu^II, Zn^II and Cd^II chloride give complexes Ni(LH)₂, Cu(LH)₂, Zn(LH₂)(Cl)₂, Cd(LH₂)(Cl)₂, respectively.     

Coordination compounds of 2-mercapto-1-methylimidazole with platinum(II), palladium(II), rhodium(III) and ruthenium(III)

Summary Complexes of 2-mercapto-1-methylimidazole (TMZ) with Pt^II, Pd^II, Rh^III and Ru^III of the general formulae Pt(TMZ)₂Cl₂, Pd(TMZ)₄Cl₂. Rh(TMZ)Cl₃ and Ru(TMZ)Cl₃ have been obtained. The thermal stabilities of the compounds were estimated by derivatographic measurements and the electron-donating atom of the measurements and the electron-donating atom of the ligand was identified from the i.r. absorbtion spectra. Lattice constants for the Pt^II and Pd^II complexes were estimated from their x-ray powder diffraction patterns.     

Complexes of N-phenyl-N′-2-furanthiocarbohydrazide with oxovanadium(IV), manganese(III), iron(III), cobalt(II), nickel(II), copper(II) and zinc(II)

A new ligand, N-phenyl-N -2-furanthiocarbohydrazide (HPhfth), and its complexes with VO^IV, Mn^III, Fe^III, Co^II, Ni^II, Cu^II and Zn^II have been prepared and characterized by elemental analyses, magnetic susceptibility measurements, i.r., n.m.r., u.v.–vis., mass and FAB mass spectral data. The room temperature e.s.r. spectra of the VO^IV, Fe^III and Cu^II complexes yield <g> values characteristic of square pyramidal VO^IV, octahedral Fe^III and square planar Cu^II, respectively. The Ni^II and Cu^II complexes semiconduct, but the Zn^II complex is an insulator at room temperature. However, the conductivity increases as the temperature increases from 303–383 K, with a band gap of 0.21–1.01 eV. HPhfth and its soluble complexes have been screened against several bacteria and fungi.     

On the nature of the chemical bond in heterobimetallic palladium(II) complexes with divalent 3<Emphasis Type="Italic">d</Emphasis> metals

The complex Pd(μ-OOCMe)₄Cu(OH₂) · 2Pd₃(μ-OOCMe)₆ was synthesized and characterized by X-ray crystallography. In the heterometallic moiety of this complex, the Pd^II and Cu^II atoms are at an extraordinary short distance (2.521(3) Å). DFT quantum-chemical calculations of the geometric and electronic structure of a series of heterobinuclear paddlewheel complexes Pd^IIM^II(μ-OOCMe)₄L (M = Zn^II, Ni^II, Cu^II, Co^II, Fe^II; L = OH₂ and NCH) and their formate analogues Pd^IIM^II(μ-OOCH)₄L (M = Zn^II, Ni^II, Fe^II) showed that the extraordinary short Pd?M distance in all these complexes is caused only by the tightening effect of carboxylate bridges rather than by the metal-metal bond. The direct Pd-M interaction becomes possible only after removal of electrons from the antibonding orbitals and formation of oxidized complexes of the [Pd^III(μ-OOCMe)₄Ni^III]²⁺ type.     

Coordination chemistry and biological activity of two tridentate ONS and NNS Schiff bases derived from S-benzyldithiocarbazate

Two tridentate Schiff bases having ONS and NNS donor sequences were prepared by condensing S-benzyldithiocarbazate (NH₂NHCSSCH₂Ph) (SBDTC) with pyridine-2-carboxaldehyde and salicylaldehyde, respectively. Complexes of these ligands with Ni^II, Zn^II, Cr^III, Co^II, Cu^II, and Sn^II were studied and characterized by elemental analyses and various physico-chemical techniques. Ni^II, Cu^II, Zn^II and Sn^II complexes were four-coordinate while the Cr^III, Sr^III and Co^III complexes were six-coordinate. The ONS Schiff base was moderately active against leukemia, while its zinc, antimony and cobalt complexes were strongly active against leukemic cells with DC₅₀ = 0.35–5.00.     

Chelatbildung mit N-unsubstituierten 1.2-Diiminliganden

Fe^II, Co^III, Ni^II, Pd^II, and Rh^III chelates with the N-unsubstituted 1-2-diimine ligands benzildiimine and 9.10-phenanthrenequinonediimine have been prepared. The compounds are characterised chemically, spectroscopically (uv, vis, ir) and polarographically. The results indicate remarkable π-back bonding in the chelates. The unusual magnetic moments of the Fe^II, Co^III and Rh^III chelates are caused by temperature-independent paramagnetism. Fe^II, Co^III, Ni^II and Cu^II chelates of the partially deprotonated phenanthrenequinone diimine are obtained.