N,N′-Dimethylthiourea Complees of Zinc,Cadmium(II), and Mercury(II)

N,N′-Dimethylthioharnstoff-Komplexe des Zn, Cd^II und Hg^II Komplexe des N,N′-Dimethylthioharnstoffs (DMTU) mit Zn–, Cd^II-und Hg^II-Halogeniden des Typs M(DMTU)₂X₂ und [HgDMTUX₂]₂ (X ? Cl, Br, J) wurden dargestellt und IR-spektroskopisch (4000-60cm^?1) sowie durch Leitfähigkeitsmessungen untersucht. Die Molekulargewichte einiger dieser Komplet in Nitrobenzol werden angegeben. Die 1:2-Komplexe Zn(DMTU)₂X₂, Cd(DMTU)₂X₂ (X ? Cl, Br, J) und Hg(DMTU)₂J₂ sind tetraedrisch, während die Komplexe Hg(DMTU)₂X₂ (X ? Cl, Br) eine pseudooktaedrische Halogen-verbrückte Konfiguration zu haben scheinen. Die 1:1 Hg^II-Komplexe [HgDMTUX₂]₂ (X ? Cl, Br, J) haben im festen Zustand eine dimere tetraedrische Halogen-verbrückte Struktur. In allen diesen Komplexen ist N,N′-Dimethylthioharnstoff über den Schwefel am Metall gebunden.     

Zinc (II), cadmium (II) and mercury (II) complexes of 2-methyl-benzoxazole

The following zinc (II), cadmium (II) and mercury (II) complexes of 2-methyl-benzoxazole (L) have been prepared and studied by conductometric and i.r. methods: MLX₂ (MCd, XCl, Br; MHg, XCl), HgL_1.5X₂ (XBr, ClO₄), ML₂X₂ (MZn, XCl, Br, I, NO₃; MCd, Hg, XI, NO₃), ZnL₃(ClO₄)₂·2H₂O, CdL₃(ClO₄)₂·3H₂O. The frequency decrease of the ligand bands at 1614 and 1573 cm⁻¹ having a ν(CN) and the increase of the ligand band at 918 cm⁻¹ having a ν(CO) contribution indicate that in the complexes the ligand is N-bonded to the metal.     

Complexes of zinc(II), cadmium(II) and mercury(II) halides with ethylenselenourea

Summary Reaction of zinc(II), cadmium(II) and mercury(II) halides with ethylenselenourea yields complexes of general formula ML₂X₂ where X = Cl, Br, I. On the basis of an i.r. comparison of these complexes and their ethylenthiourea analogues in the 4000-200 cm^–1 range, it appears that the ethylenselenourea complexes are monomeric, tetrahedral and Se-bonded to the metals. The metal-halogen and metal-ligand vibrations above 200 cm^–1 are identified.This work was supported by the National Research Council (C.N.R.) of Italy.     

Zinc(II), cadmium(II) and mercury(II) halide pyrrolidine-2-selone complexes

Summary Reaction of zinc(II), cadmium(II) and mercury(II) halides with Pyrrolidine-2-selone yields complexes of general formula ML₂X₂ (X = Cl, Br or I) which are monomeric, tetrahedral and Se-bonded to the metals. The comparison of their i.r. spectra with the spectrum of the free ligand confirms that the band at 1005 cm^–1 in Pyrrolidine-2-selone arises predominantly from the C=Se stretching vibration. The metalhalogen absorptions above 200 cm^–1 are identified.This work was supported by the National Research Council (C.N.R.) of Italy.     

Zinc(II), Cadmium(II), and Mercury(II) Complexes of 2-Methyl-benzoselenazole

The following zinc(II), cadmium(II) and mercury(II) complexes of 2-methyl-benzoselenazole (L) have been prepared and studied by conductometric and i.r. methods: MLX₂ (M ? Cd, Hg, X ? Cl, Br, I), ML_1.5X₂ (M ? Zn, X ? ClO₄(4 H₂O); M ? Hg, X ? NO₃, ClO₄), ML₂X₂ (M ? Zn, X ? Cl, Br, I, NO₃; M ? Cd, X ? NO₃, ClO₄). The ligand is N-bonded. All the anions are coordinated.     

Metal complexes of sulfur-nitrogen chelating agents. Part 12. The chemistry of nickel(II), palladium(II), cobalt(II) and copper(II) complexes of N2S2 and N3S2 donor systems

Summary Nickel(II), palladium(II), cobalt(II) and copper(II) complexes of the ligandN,N-1,2-propane-bis(methyl 2-amino-cyclopent-1-ene-dithiocarboxylate) (H₂L¹),N,N-1,3-propane-bis(methyl 2-aminocyclopent-1-ene-dithiocarboxylate) (H₂L²) andN,N-[bis(methyl 2-aminocyclopent-1-ene-dithiocarboxylate)] diethylenetriamine (H₂L³) have been synthesised. Both H₂L¹ and H₂L² form complexes of the type ML, and all but the copper(II) complexes, are square planar. In the copper(II) complexes tetrahedral distortion is significantly more with CuL². From H₂L³ square planar complexes of the type [M(HL³)X] (M=Ni, X=Cl, Br, I or SCN; M=Pd, X=Cl or Br) have been obtained in which the donor unit involved is N₂SX. The composition of the cobalt(II) and copper(II) complexes is [M(H₂L³)X₂] (X=Cl or Br) which contain the chromophore [MN₃X₂].     

Cobalt(II) and copper(II) complexes of 3-amino-5-methylisoxazole

Summary Cobalt(II) and copper(II) halide, nitrate, thiocyanate and perchlorate complexes of 3-amino-5-methylisoxazole (3-AMI) have been prepared and characterized by means of magnetic, spectroscopic and molar conductivity measurements. In Cu(3-AMI)₂X₂ compounds (X = Cl, Br, N02) the 3-AMI ligand is bridging and bidentate [N (ring), O(bonded)]. In the other derivatives it is monodentate [N(ring) bonded]. All cobalt(II) complexes have an octahedral stereochemistry, if the Co(3-AMI)₂X₂ derivatives (X = Cl, Br), which are tetrahedral, are excluded. Copper(II) complexes have generally a distorted square pyramidal stereochemistry in the solid state and in solution.     

Osmium(II)-Phthalocyanine: Darstellung und Eigenschaften von Di(acido)phthalocyaninatoosmaten(II)

Osmium(II) Phthalocyanines: Preparation and Properties of Di(acido)phthalocyaninatoosmates(II) “H[Os(X)₂Pc^2?]” (X = Br, Cl) reacts in basic medium or in the melt with (ⁿBu₄N)X forming less stable, diamagnetic, darkgreen (ⁿBu₄N)₂[Os(X)₂Pc^2?]. Similar dicyano and diimidazolido(Im) complexes are formed by the reaction of “H[Os(Cl)₂Pc^2?]” with excess ligand in the presence of [BH₄]^?. The cyclic voltammograms show up to three quasireversible redoxprocesses: E_1/2(I) = 0.13 V (X = CN), ?0.03 V (Im), ?0.13 V (Br) resp. ?0.18 V (Cl) is metal directed (Os^II/III), E_1/2(II) = 0.69 V (Cl), 0.71 V (Br), 0.83 V (CN), 1.02 V (Im) is ligand directed (Pc^2?/?) and E_1/2(III) = 1.17 V (Cl) resp. 1.23 V (Br) is again metal directed (Os^III/IV). Between the typical “B” (～16.2 kK) and “Q” (～29.4 kK), “N regions” (～34.1 kK) up to seven strong “extra bands” of the phthalocyanine dianion (Pc^2?) are observed in the uv-vis spectrum. Within the row CN > Im > Br > Cl, most of the bands are shifted slightly, the “extra bands” considerably more to lower energy in correlation with E_1/2(I). The vibrational spectra are typical for the Pc^2? ligand with D_4h symmetry. M.i.r. bands at 514, 909, 1 173 and 1 331 cm^?1 are specific for hexa-coordinated low spin Os^II phthalocyanines. In the resonance Raman (r.r.) spectra polarized, depolarized or anomalously polarized deformation and stretching vibrations of the Pc^2? ligand will be selectively enhanced, if the excitation frequency coincides with “extra bands”. With excitation at ～19.5 kK the intensity of the symmetrical Os? X stretching vibration at 295 cm^?1 (X = Cl), 252 cm^?1 (X = Im) and 181 cm^?1 (X = Br) is r.r. enhanced, too. The asymmetrical Os? X stretching vibration is observed in the f.i.r. spectrum at 345 cm^?1 (X = CN), 274 cm^?1 (X = Cl), 261 cm^?1 (X = Im) and 200 cm^?1 (X = Br).     

Zinc(II), cadmium(II) and mercury(II) complexes of 4,6-dimethyl-pyrimidine-2(1H)-one

The following zinc(II), cadmium(II) and mercury(II) complexes of 4,6-dimethylpyrimidine-2(1H)-one (L) have been prepared and investigated by conductometric,IR and Raman methods: MX₂L₂ (M = Zn, X = Cl, Br(CHCl₃, I(CHCl₃, CF₃COO; M = Cd, X = Cl, Br CF₃COO; M = Hg, X = Cl, CF₃COO), Cd₂I₄L₃, Hg₃X₆L₂ (X = Cl, Br), Hg₃X₆L₄(X = Br, I), MX₂L₄·6H₂O (M = Zn, Cd, X = CIO₄, BF₄; M = Hg, X = CIO₄. The ligand is principally bonded through the unprotonated nitrogen atom and in some complexes also through the carbonylic oxygen atom. The zinc halide complexes are tetrahedrally coordinated, the trifluoroacetate ion is coordinated as a monodentate ligand.     

Co-ordination compounds of diacetyldihydrazone and diacetylbis(monomethylhydrazone)

Summary Diacetyldihydrazone (DADH) forms only six-coordinate complexes with iron(II), cobalt(II), nickel(II) and zinc(II). In M(DADH)₂X₂ (M=Fe, X=Br or I; M=Co, X=I; M=Ni, X=Cl, Br or NCS) the ligand is chelating in the [M(DADH)₃]²⁺ cations, while in M(DADH)₂X₂ (M=Co, X=Cl or Br; M=Ni, X=Cl or Br) the ligand is probably bridging and bidentate. Diacetylbismonomethylhydrazone (DAMH), by contrast, forms predominantly tetrahedral complexes M(DAMH)X₂ (M=Fe or Co, X=Cl or Br; M=Ni, X=Br; M=Co, X=NCS; M=Zn, X=Cl, Br or NCS) and some octahedral complexes M(DAMH)₂X₂ (M=Co, X=NCS; M=Ni, X=Br). The i.r. spectra, electronic spectra and magnetic moments of the complexes are discussed.     

Zinc(II), cadmium(II) and mercury(II) complexes of neutral and deprotonated 4,6-dimethylpyrimidine-2(1H)-thione

The following zinc(II), cadmium(II) and mercury(II) complexes of neutral and deprotonated 4,6-dimethylpyrimidine-2(1H)-thione (HL) have been prepared and studied by conductometric and i.r. methods: [M(HL)₂X₂] (M  Zn, Cd, Hg; X  Cl, Br, I), [M(HL)₃]A₂·2H₂O (M  Zn, Cd; A  ClO₄ and M  Hg; A  ClO₄, BF₄, CF₃COO), M(HL)₂(CF₃COO)₂(M  Zn, Cd), ZnL₂·HL and ML₂ (M  Cd, Hg). In most of the complexes the ligand is N,S-bonded to the metal ion, the metal-nitrogen bond being stronger than the metal-sulphur one; only in the cadmium chloride and bromide complexes the ligand seems to be only N-bonded to the metal, with bridging halide ions. Most of the complexes seem to have a distorted six-coordination while to the neutral HgL₂ complex a tetrahedral [N,S]₂ coordination may be assigned.     

Copper(I), silver(I) and mercury(II) halide complexes of the 3,5-diamino-1,2,4-dithiazolium halides (thiouret hydrohalides)

Copper(I), silver(I) and mercury(II) halide complexes of the 3,5-diamino-1,2,4-dithiazolium halides (thiouret hydrohalides, DADTX): M(DADT)X₂ (M = Cu, Ag; X = Cl, Br, I), Cu(DADT)₂I₃, Ag₅(DADT)I₆ 1.33 DMF, Ag(DADT)₄I₅, Hg(DADT)₂X₄ (X = Cl, Br, I) and Hg(DADT)X₃ (X = Br, I) have been prepared and studied by conductometric and i.r. methods. The DADT⁺ ion is coordinated to the metal through its ring nitrogen atom. In the Cu(DADT)₂I₃ and Ag(DADT)₄I₅ complexes some of the DADT⁺ ions are not coordinated. The M(DADT)X₂ complexes have a (N, X_t 2X_b) pseudo-tetrahedral coordination. In the Cu(DADT)Cl₂ complex the three observed ν(CuCl) bands have frequencies inversely and linearly proportional to the CuCl distances observed in the crystal. The Hg(DADT)₂X₄ complexes have a (N₂, X₄) D_4h pseudo-octahedral coordination with the HgI₄ moiety presumably tetrahedrally distorted in the iodide.     

Zinc (II), cadmium (II) and mercury (II) complexes of 2,3-diphenyl-2,3-dehydrotetrazolium-5-thiolate (dehydrodithizone)

The following Zn(II), Cd(II) and Hg(II) complexes of 2,3-diphenyl-2,3-dehydrotetrazolium-5-thiolate (dehydrodithizone) were prepared: ML₂X₂ (M  Zn, Cd; X  Cl, Br, I, SCNM  Hg; X = SCN), HgLX₂ (X  Cl, Br, I), ML₄(BF₄)₂ (M Cd, Hg), ZnL₂SO₄. All the complexes are non-electrolytes. The i.r. and far i.r. spectra indicate that the ligand is sulphur-coordinated to the metal. The complexes have the following structures: [ML₂X₂] (M  Zn, Cd; X  Cl, Br, I) are monomeric pseudo-tetrahedral; [HgLX₂]₂ (X  Cl, Br, I) are tetrahedral dimeric sulphur-bridged; [ZnL₂(NCS)₂] and [HgL₂(SCN)₂] are monomeric tetrahedral with the thiocyanate group N-bonded for zinc (II) and S-bonded for mercury (II); [CdL₂(SCN)₂]_n has a polymeric six-coordination with bridging thiocyanate groups; [ZnL₂SO₄]_n has a polymeric six-coordination with bridging sulphate groups; [ML₄(BF₄)₂] (M  Cd, Hg) have a pseudo-octahedral coordination in which BF₄ group is coordinated to the metal through a weak MF bond.     

Solid-state vibrational spectroscopy: Part 11. An infrared and raman vibrational spectroscopic study of metal(II) halide aniline complexes

Infrared (4000?200 cm^?1) and Raman (3500?50 cm^?1) spectra are reported for metal(II) halide aniline complexes of the following stoichiometries: (MX₂an₂) (M  Co, Ni or Hg, X  Cl; M  Mn, X  Cl or Br; M  Zn or Cd, X  Cl, Br or I); (MX₂an₃) (M  Mn, X  Cl or Br; M  Ni, X  Cl); (CdCl₂an) and an assignment is proposed for all the observed bands. Low-temperature (83 K) IR spectra are also reported and it is noted that whilst the aniline ring and CH mode values are virtually insensitive to temperature, the NH₂ rocking and metal-ligand stretching mode values increase with decreasing temperature, whilst the NH₂ stretching mode values decrease with decreasing temperature.     

Complexes of IIB Metal Halides with N,N-Diethylbenzenecarbothioamide crystal structure of [Hg{C6H5C(S)N(C2H5)2}I2]2

Complexes having the empirical formulae M(DEBCTA)₂X₂ (M = Zn or Cd, X = Br or I, DEBCTA = N,N-diethylbenzenecarbothioamide), Zn(DEBCTA)Cl₂, Cd₂(DEBCTA)Cl₄ and Hg(DEBCTA)X₂ (X = Cl, Br or I) were made by reaction of zinc, cadmium or mercury dihalides in ethanol or 1,2-dichloroethane. All complexes have been characterized by elemental analysis, conductance and molecular weight measurements and by infrared and ¹H-NMR spectral studies. In addition, the structure of [Hg(DEBCTA)I₂]₂ has been determined by single-crystal X-ray crystallography and refined to a conventional R factor of 0.097. The compound crystallizes in the monoclinic space group P2₁/n with a = 1383.9(2), b = 834.3(1), c = 1418.2(2) pm, β = 101.03(1)° and Z = 2. The molecule was found to have a dimeric structure involving two asymmetrical iodine bridges in which the Hg atom lies a tetrahedral environment and the ligands lie mutually trans with respect to one another.     

Zinc(II), cadmium(II) and mercury(II) complexes of 4-amino-benzophenone

The following zinc(II), cadmium(II) and mercury(II) complexes of 4-amino-benzophenone (L) have been prepared and studied by i.r. and electronic spectra: 2MX₂·3L (M=Zn, Cd; X=Cl, Br), 3ZnI₂·2L, 2ZnI₂·L, MX₂·L (M=Cd, X=I; M=Hg, X=Cl, Br). Infrared spectra show that in the zinc complexes the ligand is principally bonded through the aminic nitrogen atom and in the cadmium and mercury(II) complexes through the carboxylic oxygen atom.     

Ruthenium(II)-Phthalocyanine: Darstellung und Eigenschaften von Di(halogeno)phthalocyaninatoruthenat(II)

Ruthenium(II) Phthalocyanines: Preparation and Properties of Di(halo)phthalocyaninatoruthenate(II) [Ru(Py)₂Pc^2?] reacts with molten (ⁿBu₄N)X forming stable, green (ⁿBu₄N)₂[Ru(X)₂Pc^2?] (X = Cl, Br). The cyclovoltammogram shows a quasireversible redoxprocess for the metal oxidation at E_1/2(I) = ?0.02 V (X = Cl) resp. 0.05 V (X = Br) and for the first ringoxidation at E_1/2(II) = 0.70 V. The typical π-π*-transitions (B < Q < N) of the phthalocyanine dianion (Pc^2?) are observed in the uv-vis spectrum. With respect to Ru^III phthalocyanines B is shifted significantly to higher, Q, N to lower energy. The strong extra-band at 24.2 kK is diagnostic for these Ru^II phthalocyanines. The vibrational spectra are typical for the Pc^2? ligand with D_4h symmetry, too, and bands at 513, 909, 1 171 und 1 329 cm^?1 in the m.i.r. spectrum are specific for hexa-coordinated low spin Ru^II. In the Raman spectrum with excitation at ～480 nm the intensity of the totally symmetrical Ru? X stretching vibration at 266 cm^?1 (X = Cl) resp. 168 cm^?1 (X = Br) together with a progression of up to three overtones is selectively resonance Raman enhanced. The asymmetrical Ru? X stretching vibration is observed in the f.i.r. spectrum at 272 cm^?1 (X = Cl) resp. 215 cm^?1 (X = Br).     

N,N-Dimethylbenzenocarbothioamide Complexes of IIB metal halides

The complexes Zn(DMBCTA)X₂ (X = Cl, Br or I), Cd₇(DMBCTA)₄Cl₁₄, Cd(DMBCTA)X₂ (X = Br or I) and Hg(DMBCTA)X₂ (X = Cl, Br or I; DMBCTA = N,N-Dimethylbenzenocarbothioamide) were isolated and characterized by elemental analysis, conductance and molecular weight measurements, and IR, Raman, and ¹H NMR spectroscopy.     

Ruthenium(II)-Phthalocyaninate(2–): Darstellung und Eigenschaften von Acido(carbonyl)phthalocyaninato(2–)ruthenat(II), [Ru(X)(CO)Pc2−]− (X = Cl,Br, I,NCO, NCS,N3)

Ruthenium(II) Phthalocyaninates(2–): Synthesis and Properties of (Acido)(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) (ⁿBu₄N)[Ru(OH)₂Pc^2?] is reduced in acetone with carbonmonoxid to blue-violet [Ru(H₂O)(CO)Pc^2?], which yields in tetrahydrofurane with excess (ⁿBu₄N)X acido(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) isolated as red-violet, diamagnetic (ⁿBu₄N) complex salt. The UV-Vis spectra are dominated by the typical π-π* transitions of the Pc^2? ligand at approximately 15100 (B), 28300 (Q₁) und 33500 cm^?1 (Q₂), only fairly dependent of the axial ligands. v(C? O) is observed at 1927 (X = I), 1930 (Cl, Br), 1936 (N₃, NCO) 1948 cm^?1 (NCS), v(C? N) at 2208 cm^?1 (NCO), 2093 cm^?1 (NCS) and v(N? N) at 2030 cm^?1 only in the MIR spectrum. v(Ru? C) coincides in the FIR spectrum with a deformation vibration of the Pc ligand, but is detected in the resonance Raman(RR) spectrum at 516 (X = Cl), 512 (Br), 510 (N₃), 504 (I), 499 (NCO), 498 cm^?1 (NCS). v(Ru? X) is observed in the FIR spectrum at 257 (X = Cl), 191 (Br), 166 (I), 349 (N₃), 336 (NCO) and 224 cm^?1 (NCS). Only v(Ru? I) is RR-enhanced.     

Complexes of zinc,cadmium and mercury(II) with the zwitter-ionic form of NN′-ethylenebis (salicylideneimine)

The Schiff base NN′-ethylenebis(salicylideneimine), H₂ salen reacts with hydrous and anhydrous Zinc, Cadmium and Mercury(II) salts to give complexes M(H₂ salen)X₂·nH₂O (M = Zn, Cd, Hg; XCl, Br, I, NO₃; MZn, X₂SO₄; n = 0?2). Spectroscopic and other evidence indicated that; (i) halide and sulphate are coordinated to the metal ion, whereas the nitrate group is ionic in mercury nitrate compound and covalently bonded in zinc and cadmium nitrato complexes, (ii) the Schiff base is coordinated through the negatively charged phenolic oxygen atoms and not the nitrogen atoms, which carry the protons transferred from phenolic groups on coordination, (iii) therefore the coordination numbers suggested are 4-, in mercury and 4- or 6- in zinc and cadmium Schiff base complexes.