Synthesis Of N,N′-Bis(8-Quinolyl)-Oligo-Methylene-Diamines from 8-Aminoquinolines

Various N′,N-bis(8-quinolyl) trimethylenediamines 3a-3e have been prepared from the corresponding 8-aminoquinolines 1a-1e by direct N-alkylation with 1, 3-dibromopropane in fair yield (25-51%). N. N′-bis(8-quinolyl) ethylenediamines, 3f and 3g, and N,N′-bis(8-(6-methoxyquinolyl) ]tetramethylenediamine. 3h, may only be synthesized in poor yield via the corresponding oxalamides and succinamide.     

N,N′-(disubstitutedmethylene)bisacrylamides: Preparation and polymerization

Preparative methods for the previously unreported N,N′-(disubstitutedmethylene)-bisacrylamides are presented. The solubility and thermal stability of these new bisamides are compared to the well known N,N′-methylenebisacrylamide. N,N′-Isopropyl-idenebisacrylamide, one of these new compounds, readily copolymerizes with a variety of vinyl monomers. It forms high molecular weight copolymers by the conjugate polyaddition of alkanedithiols or piperazine.     

Syntheses of N,N′-Bis(salicylideneiminoethyl)oxamidatodicopper(II), N,N′-Bis(salicylideneiminoisopropyl)-oxamidatodicopper(II), and N,N′-Bis(2-pyridylideneiminopropyl)oxamidatodicopper(II) Nitrate and Corresponding Perchlorate

Reactions of coordinated functional groups were carried out as follows: The product formed by reaction of A-1a

1 The four new complexes are shown as A-3a, A-3b, B-3a, and B-3b (cf. Fig. 1), and other related complexes are shown as A-1a, A-1b, A-2a, A-2b, B-n, B-1, B-4, and B-5 (cf. Fig. 2)

or A-1b with copper(II), reacts with salicylaldehyde to give A-3a or A-3b, respectively. And the product formed by reaction of B-1 with copper(II), reacts with pyridine-2-aldehyde to give B-3a or B-3b. The four binuclear copper(II) complexes thus isolated as the new compounds have been characterized by elemental analyses, u.v. and i.r. spectra, magnetic susceptibility, and electronic conductivity measurements. Attempts to exchange the reactants with one another were unsuccessful.     

Dissociation Kinetics of Nickel (II), Zinc (II) and Cadmium (II) Complexes of 1,7-Diaza-4,10,13-trioxacyclopentadecane-N,N′-diacetic Acid and 1,10-Diaza-4,7,13,16-tetraoxacyclooctadecane-N,N′-diacetic Acid

The dissociation kinetics of the complexes of nickel(II), zinc(II) and cadmium(II) of 1,7-diaza-4,10,13-trioxacyclopentadecane-N,N′-diacetic acid (K21DA) and 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N′-diacetic Acid (K22DA) were studied in constant ionic strength aqueous medium with various [H⁺]-range, i.e., (0.88?53.9) × 10^?5 M and (0.5?7.5) × 10^?3 M. Copper(II) was used as the scavenger of free ligand and the rates of dissociation of these complexes have been found to be independent of (Cu²⁺]. All the complexes exhibit acid-independent and acid-dependent pathways. For NiK21DA, CdK21DA and CdK22DA complexes, the acid-dependent rates are linear functions of [H⁺]. For NiK22DA and ZnK21DA complexes, a saturation kinetics is observed, i.e., [H⁺]-dependence at low [H⁺] and [H⁺]-independent at high [H⁺]. The rationalization of such different observations is proposed to be due to difference in complex solution structures rather than the thermodynamic stabilities. Influence of acetate content in the buffer, temperature, and total electrolyte concentration on the rate of dissociation has also been investigated and discussed.     

Syntheses,Spectra, Thermal Studies and Crystal Structures of Vitamin B13 Complexes of Nickel(II) with N,N,N′,N′‐Tetramethylethylenediamine and 2,2‐Dimethylpropane‐1,3‐diamine

Two nickel(II) complexes of vitamin B13 (H₃Or) with N,N,N′,N′‐tetramethylethylenediamine (tmen) and 2,2‐dimethylpropane‐1,3‐diamine (dmpen) were synthesized and characterized by means of elemental and thermal analyses, magnetic susceptibility, and IR and UV/Vis spectroscopic studies. The crystal structures of mer‐[Ni(HOr)(H₂O)₂(tmen)] · H₂O ( 1 ) and [Ni(HOr)(dmpen)₂] ( 2 ) were determined by using single‐crystal X‐ray diffraction. In the complexes, which crystallize in the triclinic system (space group for 1 ) and the monoclinic system (space group P2₁/c for 2 ), the Ni^II ions exhibit a distorted octahedral coordination. Ni^II ions are chelated by the deprotonated nitrogen atom of the pyrimidine ring and the oxygen atom of the carboxylate group, the distorted octahedral coordination completed by one tmen and two aqua ligands for 1 or two dmpen ligands for 2 .     

Thermodynamic, crystallographic and solvent extraction properties of cobalt(II), nickel(II) and copper(II) complexes of ethylenediamine- N,N,N′,N′-tetraacetanilide

Complexes of ethylenediamine-N,N,N′,N′-tetraacetanilide (edtan, C₃₄H₃₆N₆O₁₄) with cobalt(II), nickel(II) and copper(II) in the solid state and in solution are reported for the first time. Thermodynamic data (stability constant, and derived Gibbs energy, enthalpy and entropy changes)for the 1 : 1 complexation of edtan with the metal ions at 298.15 K in water-saturated butan-1-ol gave the selectivity sequence log₁₀K_s; Ni²⁺, 4.56±0.02; Cu²⁺, 4.41±0.01; Co²⁺, 4.18±0.04 as found from microcalorimetric titration studies. The entropies suggested that the structure of the 1 : 1 complex with copper(II) contains fewer chelate rings than those for nickel(II) and cobalt(II) (δ_cS⁰ : Cu-21.4, Co 5.7, Ni 3.9 J mol⁻¹K⁻¹). Solid complexes of the metal ions with edtan and perchlorate as the counter anion were prepared. For each, a complex with a 1 : 1 metal: edtan stoichiometry with non-coordinated perchlorate was isolated. The X-ray structure of [Cu(edtan)(H₂O)][ClO₄]₂·1.5H₂O (1) revealed a six-coordinate Cu centre with edtan acting as pentadentate ligand (2N, 3O) with the coordination sphere completed by an oxygen atom from water. In striking contrast to the Cu complex, the Co centre in [Co(edtan)(H₂O)][ClO₄]₂·H₂O·0.5C₂H₅OH (2) is seven-coordinate with hexadentate edtan (2N, 4O) and one coordinated water molecule. There is thus an excellent confirmation of the results obtained from the microcalometric study in that edtan forms four chelate rings to Cu but five to Co in the solid state. The ability of the ligand to extract metal ions from water to the water-saturated butan-1-ol phase was assessed from distribution data as a function of the aqueous phase hydrogen ion concentration and of the ligand concentration in the organic phase. The data showed that Cu²⁺ is selectively extracted over a wide range of aqeous phase hydrogen ion concentrations.     

Kristall- und Molekülstruktur von N,N′-o-Phenylen-bis-(N″,N′-diethyl-N‴-benzimidoyl-thioureato)nickel(II)

Crystal and Molecular Structure of N,N′-o-Phenylen-bis-(N″,N″-diethyl-N?-benzimidoyl-thioureato)nickel(II) The structure of the title compound has been determined by an X-ray structure analysis. The compound crystallizes in the monoclinic space group C2/c with a = 38.896, b = 14.326, c = 11.121 Å, β = 102.33° and Z = 8. The solution of the structure was performed by Patterson methods. The final R value was R = 0.053 for 2260 observed reflections. The coordination geometry is nearly planar. The ligator atoms show as a necessity a cis arrangement. The chelate rings deviate from planarity. The phenyl rings and the phenylene fragment are significantly twisted in respect to the chelate rings.     

Copper(II) Complexes of N,N′-Bis-βCarbamoylethyl) Ethylenediamine in Aqueous Solution

The interactions of the ligand N, N -bis-(β-carbamoylethyl)-ethylenediamine (BCEN) with copper (II) in aqueous solution have been investigated by potentiometric and spectrophotometric techniques. The two protonation constants of the ligand at 25° in 0.2 M NaNO₃are 10^5-51and 10^5-44 The quantitative equilibrium studies of the stepwise reactions which precede the formation of CuBCEN²⁺ and the Cu-O to Cu-N bond rearrangements at the two amide sites are described in detail. Electronic spectra of the copper (II) chelates formed are measured and discussed.     

[N,N′‐Bis(3‐aminopropyl)ethylenediamine‐κ4N,N′,N′′,N′′′](trithiocyanurato‐κ2N,S)zinc(II) ethanol solvate

In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ⁴N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ²N,S]­zinc(II) ethanol sol­vate, [Zn(C₈H₂₂N₄)₂(C₃HN₃S₃)]·C₂H₆O, the Zn^II atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH²⁻) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.     

Complexes of diorganotin(IV) dihalides with N,N′-dimethyl-2, 2′-bisimidazole

Adducts of N, N′ -dimethyl-2, 2′-bisimidazole (DMBIm) with diethyl- and dibutyl-tin(IV) dihalides (Cl, Br) have been isolated and characterized. IR data for [SnR₂X₂(DMBIm)] compounds are in keeping with a six-coordinate tin atom with DMBIm acting as a bidentate ligand, whereas in [(SnR₂X₂)₂(DMBIm)] the tin is five-coordinate and DMBIm acts as a bridging ligand. Measurements of conductivity in acetonitrile show the adducts to behave as non-ionogens in this solvent. NMR data show them to undergo dissociation in CDCl₃.     

New seven-coordinate thiourea and N,N,N′,N′-tetramethylthiourea complexes of molybdenum(II) and tungsten(II)

The compounds [MI₂(CO)₃(NCMe)₂] (M = Mo or W) react with one equivalent of thiourea (tu) in MeOH or N,N,N′,N′-tetramethylthiourea (tmtu) in CH₂Cl₂ at room temperature to initially afford the monoacetonitrile compounds [MI₂(CO)₃(NCMe)L] (L = tu or tmtu) which rapidly transform to the isolated iodide bridged dimers, [M(μ-I)I(CO)₃L]₂ with loss of acetonitrile. Reaction of [WI₂(CO)₃(NCMe)₂] with two equivalents of tu or tmtu gave the expected mononuclear seven-coordinate compounds [WI₂(CO)₃L₂]. However, reaction of [MoI₂(CO)₃(NCMe)₂] with two equivalents of tu or tmtu rapidly affords the iodide-bridged dimers [Mo(μ-I)I(CO)₂L₂]₂ with loss of carbon monoxide from [MoI₂(CO)₃L₂]. The low temperature (−70°C) ¹³C NMR spectrum of [Mo(μ-I)I(CO)₂ {SC(NMe₂)₂}₂]₂ suggests the complex is based on two capped octahedra with a carbonyl ligand capping each octahedral face.     

Binuclear Copper(II) Complexes. N,N′-bis(3-aminopropyl)-oxamidatocopper(II) coordinated as a bidentate ligand

Four new binuclear copper(II) complexes having sub-normal magnetic moment have been synthesized by reaction of N, N′-bis(3-aminopropyl)-oxamidatocopper(II) with another copper(II) compound such as mono- and bis-(2,2′-bipyridine)-copper(II) nitrate, cupric mono-malonate, or cupric chloride. One of them, [Cu₂(APxd)(bipy)₂](NO₃)₂(cf. Fig. 2), was recognized to be a binuclear complex in which each copper(II) ion has a five-coordinated environment. The data from analyses, IR and electronic spectra, magnetic susceptibility measurements, and conductivity measurements were used to establish the structures.     

A complex containing three different kinds of Ru—N bonds: ethoxydinitronitrosyl(N,N,N′,N′‐tetramethylethylenediamine‐κ2N,N′)ruthenium(II)

The octahedral title compound, [Ru(C₂H₅O)(NO)(NO₂)₂(C₆H₁₆N₂)], crystallizes in the rhombohedral space group P3₁ with an ethoxy ligand axially coordinated trans to the nitro­syl ligand. The Ru^II ion is equatorially coordinated by a tetramethylethylenediamine group acting as a bidentate ligand, and to two nitro moieties whose planes are tilted with respect to the mean equatorial plane. Each nitro­gen ligand bonded to the metallic centre has a different hybridization state.     

N,N′,N′′,N′′′‐Tetraethylterephthalamidinium bis(tetrazolate)

The crystal structure of the title 2:1 salt of tetrazole and a substituted terephthal­amidine, C₁₆H₂₈N₄²⁺·2CHN₄^?, contains an infinite network of hydrogen bonds, with short N?N distances of 2.820 (2) and 2.8585 (19) Å between the tetrazolate anion and the amidinium cation. Involvement of the lateral N atoms of the tetrazole in the hydrogen bonding appears to be a typical binding pattern for the tetrazolate anion.     

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.     

Dimeres N-Lithium-N′,N′-bis(dimethylphenylsilyl)- und trimeres N,N′-Dilithium-N,N′-bis(dimethylphenylsilyl)hydrazid – Synthesen,Strukturen und Reaktionen

Dimeric N-Lithium-N′,N′-bis(dimethyphenylsilyl)- and trimeric N,N′-Dilithium-N,N′-bis(dimethylphenylsilyl)hydrazide – Syntheses, Structures, and Reactions Dilithiated hydrazine reacts with two equivalents chlorodimethylphenylsilane to the isomeric bis(silyl)hydrazines 1 a and 1 b . Reactions of 1 a / 1 b with one and two equivalents n-butyllithium lead to the lithium derivatives 2 and 4 . The crystal structure analyses of 2 and 4 are reported. 2 forms with difluorodiisopropylsilane the tris(silyl)hydrazine 3 . The tetrakis(silyl)hydrazines 5 and 6 are formed in reactions of 4 with trifluoromethylsilane and tetrafluorosilane.     

Nickel(II) N‐Benzyl‐N‐methyldithiocarbamato Complexes as Precursors for the Preparation of Graphite Oxidation Accelerators

The nickel(II) N‐benzyl‐N‐methyldithiocarbamato (BzMedtc) complexes [Ni(BzMedtc)(PPh₃)Cl] ( 1 ), [Ni(BzMedtc)(PPh₃)Br] ( 2 ), [Ni(BzMedtc)(PPh₃)I] ( 3 ), and [Ni(BzMedtc)(PPh₃)(NCS)] ( 4 ) were synthesized using the reaction of [Ni(BzMedtc)₂] and [NiX₂(PPh₃)₂] (X = Cl, Br, I and NCS). Subsequently, complex 1 was used for the preparation of [Ni(BzMedtc)(PPh₃)₂]ClO₄ ( 5 ), [Ni(BzMedtc)(PPh₃)₂]BPh₄ ( 6 ), and [Ni(BzMedtc)(PPh₃)₂]PF₆ ( 7 ). The obtained complexes 1 – 7 were characterized by elemental analysis, thermal analysis and spectroscopic methods (IR, UV/Vis, ³¹P{¹H} NMR). The results of the magnetochemical and molar conductivity measurements proved the complexes as diamagnetic non‐electrolytes ( 1 – 4 ) or 1:1 electrolytes ( 5 – 7 ). The molecular structures of 4 and 5· H₂O were determined by a single‐crystal X‐ray analysis. In all cases, the Ni^II atom is tetracoordinated in a distorted square‐planar arrangement with the S₂PX, and S₂P₂ donor set, respectively. The catalytic influence of selected complexes 1 , 3 , 5 , and 6 on graphite oxidation was studied. The results clearly indicated that the presence of the products of thermal degradation processes of the mentioned complexes has impact on the course of graphite oxidation. A decrease in the oxidation start temperatures by about 60–100 °C was observed in the cases of all the tested complexes in comparison with pure graphite.