Synthesis and magnetic properties of copper (II)-lanthanoid (III) binuclear complexes with N,N′-bis(3-aminopropyl) oxamido ligand

Six novel μ-oxamido binuclear complexes, namely Cu(axpn)Ln(L)₂(ClO₄)₃ (Ln: Eu, Gd, Tb, Nd, Ho, Er), where oxpn is N,N'-bis(3-aminopropyl) oxamido, L denotes 5-nitro,10-phenanthroline (abbreviated as NO₂-phen), have been synthesized and characterised. The magnetic susceptibility of complexes Cu(oxpn)Gd(NO₂-phen)2(ClO₄)₃.2H₂O was measured over the 4–300 K and the observed data were successfully simulated by equation based on spin Hamiltonian operator (H = -2J₁ · S₂), giving the exchange integral J(Cu-Gd)=-1.62 cm^?1. This indicates a weak antiferromagnetic interaction between the Cu(II) and Gd(III) ions.     

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.     

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.     

Crystal structure of (N,N,N′,N′-tetramethyl-1,2-diaminoethane)(1,1,1-trifluoro-6-methyl-2,4-heptanedionato)copper(II) perchlorate

The solvatochromic compound [Cu(tfmh)Me₄en]ClO₄ (tfmh^? denotes the anion of 1,1,1-trifluoro-6-methyl-2,4-heptanedione) was prepared and its structure has been determined from three-dimensional X-ray diffraction data. The structure consists of discrete [Cu(tfmh)Me₄en]⁺ monomeric units and perchlorate ions. The copper(II) ion is surrounded by the two nitrogen atoms of the diamine molecule and the two oxygen atoms of the β-dionato anion. The N,N,N′,N′-tetramethyl-1,2-diaminoethane, Me₄en, coordinates as bidentate ligand through the nitrogen atoms and adopts the gauche conformation and λ configuration. The CuN₂O₂ chromophore is virtually planar. The compound crystallizes in the monoclinic system (space group P2₁/c) with a = 11.9520(2), b = 14.6600(2), c = 17.2240(4) Å, β = 135.72(2)°, Z = 4 and V = 2107.01(7) ų.     

Complex of N,N′,N′,N‴-tetrakis[2-diphenylphosphorylethyl]-1,4,7,10-tetraazacyclododecane with copper (II) perchlorate. Synthesis,structure, and conformational analysis

1,4,7,10-Tetraazacyclododecane having β-ethylphosphoryl pendant groups on the nitrogen atoms can form a complementary ligand for the Cu cation. It gives rise to a square pyramidal complex of [CuL]²⁺ compositions, the ligand entering this complex with a slight energy strain. © 1996 John Wiley & Sons, Inc.     

The hydrogen‐bonded dimers of N,N′,N′′‐tricyclohexylphosphoric triamide in new tin(IV) and copper(II) complexes

In the new tin(IV) and copper(II) complexes, cis‐dichlorido‐trans‐dimethyl‐cis‐bis(N,N′,N′′‐tricyclohexylphosphoric triamide‐κO)tin(IV), [Sn(CH₃)₂Cl₂(C₁₈H₃₆N₃OP)₂], (I), and trans‐diaquabis(N,N′,N′′‐tricyclohexylphosphoric triamide‐κO)copper(II) dinitrate–N,N′,N′′‐tricyclohexylphosphoric triamide (1/2), [Cu(C₁₈H₃₆N₃OP)₂(H₂O)₂](NO₃)₂·2C₁₈H₃₆N₃OP, (II), the N,N′,N′′‐tricyclohexylphosphoric triamide (PTA) ligands exist as hydrogen‐bonded dimers via P=O...H—N interactions around the metal center. The asymmetric unit in (I) consists of one complete complex molecule located on a general position. The Sn^IV coordination geometry is octahedral with two cis hydrogen‐bonded PTA ligands, two cis chloride ligands and two trans methyl groups. The asymmetric unit in (II) contains one half of a [Cu(PTA)₂(H₂O)₂]²⁺ dication on a special position (site symmetry for the Cu atom), one nitrate anion and one free PTA molecule, both on general positions. The complex adopts a square‐planar trans‐[CuO₂O₂] coordination geometry, with the Cu^II ion coordinated by two PTA ligands and two water molecules. Each of the noncoordinated PTA molecules is hydrogen bonded to a neighboring coordinated PTA molecule and an adjacent water molecule; the phosphoryl O atom acts as a double‐H‐atom acceptor. The P atoms in the PTA ligands of both complexes and in the noncoordinated hydrogen‐bonded molecules in (II) adopt a slightly distorted tetrahedral environment.     

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.     

[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.     

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.     

Reaction of N,N′-carbonyldiimidazole and N,N′-thionyldiimidazole with carbonyl compounds: a new imidazole transfer reaction

Ketones and aldehydes undergo facile addition reaction with N,N′-thionyldiimidazole to give the monoimidazole and the diimidazole.     

Solvation of polymeric organolithium compounds. Heats of interaction of tetrahydrofurans and N,N,N′,N′-tetramethylethylenediamine (TMEDA) with poly(butadienyl)lithium

The enthalpies of interaction of tetrahydrofuran, 2,5-dimethyltetrahydrofuran and N,N,N′,N′-tetramethylethylenediamine (TMEDA) with 0.02M benzene solutions of poly(butadienyl)lithium (M _N～4,000) were measured as a function of R([base]/[Li]) using highdilution, solution calorimetry at 25°C. At low R values (ca. 0.2) the enthalpy of interaction of THF ( — 6.1 kcal/mol) is only 1.5 kcal/mol more exothermic than with 2,5-dimethyltetrahydrofuran and both decrease rapidly with increasing R value. These results indicate that this coordination process is much less sensitive to the steric requirements of the base than analogous processes for poly(isoprenyl)lithium and poly(styryl)lithium. The concentration dependence for the enthalpy of interaction with TMEDA falls off precipitously with increasing R values from an initial value of ?12.4 kcal/mol at R = 0.14. These results suggest either a higher degree of association or a less favorable dissociation equilibrium constant for poly(butadienyl)lithium versus poly(isoprenyl)lithium.     

Synthesis,crystal structures,and magnetic properties of two cyano-bridged tungstate(V)-manganese(II) bimetallic magnets

The reaction of manganese acetate with octacyanotungastate in an aqueous solution of concentrated acetic acid gives two new three-dimensional cyano-bridged manganese(II)-tungstate(V) bimetallic assemblies, [Mn(II)(2)(H(2)O)(2)(CH(3)COO)][W(V)(CN)(8)].2H(2)O (1) (tetragonal space group I4/mcm, a = b = 11.9628(9) A, c = 13.367(2) A, and Z = 4) and Cs(I)(0.5)Mn(II)(2)[W(V)(CN)(8)](CH(3)CO(2))(1.5).H(2)O (2) (monoclinic space group C2/c, a = 16.274(2) A, b = 22.948(6) A, c = 13.196(1) A, beta = 128.040(6) degrees, and Z = 8). In complex 1, W(V)(CN)(8) adopts a square antiprismatic geometry, and each CN group coordinates to the Mn(II) ions forming W-Mn(4)-W-Mn(4)-...columnar linkages where four sites on the Mn(II) ion with octahedral geometry are occupied by CN groups. The columns are parallel and interlock, yielding a network structure. Complex 2 contains two different coordination geometries for W(V)(CN)(8), namely, square antiprismatic and dodecahedral. The columnar structures appear also in 2, where the Mn(II) ions in two different environments provide three and four coordinated sites to the CN groups. The columns are bridged by both dodecahedral W(V)(CN)(8) groups and acetates. Cs ions were intercalated in the lattice by the formation of short attractive contacts with the acetates. The field-cooled magnetization, ac susceptibility, and the field dependence of magnetization measurements show that both 1 and 2 are ferrimagnets with ordering temperatures 40 and 45 K, respectively. The investigation of the magnetostructural correlation shows that the ferrimagnetic ordering in 1 and 2 are attributed to the dominant antiferromagnetic exchange pathways d(z)2(W)-d(x')(y')(Mn) and d(x)2(-y)2(W) - d(x')(y')(Mn).     

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′‐Tetraalkylaminoazoxybenzene Derivatives; Convenient Synthesis and Mechanistic Study

N,N,N′,N′‐tetraalkyaminoazoxybenzene derivatives were conveniently prepared by the coupling of N,N‐dialkylnitrosoaniline in the presence of acetone and KOH. The reaction mechanism was proposed and investigated, and the structure of compound 3b was also confirmed by single crystal X‐ray diffractometry.     

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.     

Synthesis and characterization of N-phenylated aromatic polyureas from N,N′ -dichloroformyl-p-dianilinobenzene and N,N′ -bistrimethylsilyl-diamines

NovelN-phenylated aromatic polyureas having inherent viscosities of 0.13–0.35 dL/g were synthesized by the solution polycondensation of N,N′-dichloroformyl-p-dianilinobenzene with N,N′-bistrimethylsilyl derivatives of bis(4-aminophenyl)ether, piperazine, and p-dianilinobenzene in sulfolane. Except the polyurea containing piperazine unit, the other polyureas were amorphous and readily soluble in a variety of organic solvents such as tetrahydrofuran. The polyurea derived from p-dianilinobenzene, which has no vulnerable hydrogen on the urea linkage, did not melt below 350°C and was stable up to 450°C in air.     

Chlorido[N,N′‐dibenzyl‐N′′‐(trichloroacetyl)phosphoramidato‐κ2O,O′](1,10‐phenanthroline‐κ2N,N′)copper(II)

In the title complex, [Cu(C₁₆H₁₆Cl₃N₃O₂P)Cl(C₁₂H₈N₂)], the Cu^II cation presents a square‐pyramidal environment, where the CuO₂N₂ base is formed by two O atoms from carbonyl and phosphoryl groups, and by two N atoms from a 1,10‐phenanthroline molecule. A coordinated Cl atom occupies the apex. N—H...Cl hydrogen bonds link the molecules into one‐dimensional chains. The trichloromethyl group is rotationally disordered over two positions, with occupancies of 0.747 (7) and 0.253 (7).     

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.