Reactions of 2-hydroxy-5-(1-adamantyl)benzene-1,3-dicarbaldehyde with ethane-1,2-diamine, trans-cyclohexane-1,2-diamine, and N-(2-aminoethyl)ethane-1,2-diamine

Reactions of 2-hydroxy-5-(1-admantyl)benzene-1,3-dicarbaldehyde with ethane-1,2-diamine, transcyclohexane-1,2-diamine, and N-(2-aminoethyl)ethane-1,2-diamine were studied in strongly dilute solution and under conditions of template synthesis in the presence of H₃BO₃. The effects of reaction conditions and initial diamine structure on the cyclocondensation process were determined. Selective [3 + 3]-cyclocondensation of 2-hydroxy-5-(1-admantyl)benzene-1,3-dicarbaldehyde with trans-cyclohexane-1,2-diamine and [2 + 2]-cyclization with N-(2-aminoethyl)ethane-1,2-diamine were performed in chloroform in the presence of H₃BO₃. The first representative of adamantylcalixsalens was synthesized.     

Coordination compounds of cobalt, nickel, copper and zinc with thiosemicarbazone and 3-phenylpropenal semicarbazone

Hydrates of 3-phenylpropenal thiosemicarbazone (HL·H₂O) and semicarbazone (HL′·H₂O) react in methanol with cobalt, nickel, copper, and zinc chlorides, nitrates, and acetates to form coordination compounds MX₂·2HL·nSolv [M = Co, Ni, Cu, Zn; X = Cl, NO₃; HL = C₆H₅CH=CH-CH=N-NHC(O)NH₂; n = 0–3; Solv = H₂O, CH₃OH], CuX₂·HL·nH₂O [M = Ni, Cu; n = 0, 1], ML₂·nH₂O and ML′·nH₂O [M = Co, Ni, Zn; HL′ = C₆H₅CH=CH-CH=N-NHC(O)NH₂; n = 0–3]. In the presence of amines (A = C₅H₅N, 2-CH₃C₅H₄N, 3-CH₃C₅H₄N, and 4-CH₃C₅H₄N) these reactions yield the complexes Cu(A)LCl·CH₃OH and M(A)LX·nH₂O [M = Cu, Ni; X = Cl, NO₃; n = 0–2]. The copper complexes with the amine ligands are of polynuclear structure, and other complexes are monomeric. Carbazones (HL and HL′) are included in the complexes as bidentate N,S-and N,O-ligands. The thermolysis of the complexes involves the stages of removing solvent crystallization molecules (70–90°C), deaquation (150–170°C), and full thermal decomposition (500–580°C).     

Coordination compounds of cobalt,nickel, copper,and zinc with 2-bromo-3-phenylpropenal benzoylhydrazone and thiosemicarbazone

By X-ray structural analysis the crystal structure of 2-bromo-3-phenylpropenal benzoylhydrazone (HL) was determined. The molecule is not flat. In the crystal the HL molecules form infinite chains with reciprocal van der Waals interaction. 2-Bromo-3-phenylpropenal hydrazone (HL) and thiosemicarbazone (HL′) react with cobalt, nickel, copper and zinc chlorides, nitrates and acetates to form coordination compounds of the composition Cu(HL)(L)₂ [HL = C₆H₅-CH=CBr-CH=N-NH-C(O)-C₆H₅], MX₂·2 HL′·nH₂O [M = Co, Ni, Cu, Zn; X = Cl, NO₃, HL′ = C₆H₅-CH=CBr-CH=N-NH-C(S)-NH₂; n = 0–3], MX₂·HL·n H₂O [M = Ni, Cu; n = 0, 1], and ML′₂·nH₂O [M = Co, Ni, Zn; n = 0–3]. The same reactions in the presence of amines (A = C₅H₅N, 2-CH₃C₅H₄N, 3-CH₃C₅H₄N, 4-CH₃C₅H₄N) afford complexes of the composition CuALCl and MALX·n H₂O [M = Cu, Ni; X = Cl, NO₃; n = 0–2]. Structure of the coordination node in the amine-containing copper derivatives is polynuclear, in complexes Cu(HL)(L)₂ is octahedral, in other compounds it is tetrahedral. The azomethines (HL and HL′) in these complexes behave as bidentate N,O and N,S ligands. Thermolysis of the complexes includes a step of dehydration (60–90°C) and complete thermal decomposition (430–590°C).     

基于双吡啶基双西佛碱通过氢键相互作用形成的有机超分子晶体

合成了双吡啶双西佛碱(bpbd)有机分子，并用该分子进行了超分子网络晶体的组装．X射线单晶结构分析表明：在bpbd晶体中存在着分子间氢键相互作用，该氢键由吡啶环上的N原子和西佛碱H—C—N基团上的H原子相互作用而成．每一个bpbd分子同另外4个bpbd分子通过氢键相连，构成了二维网状结构；在bpbd晶体中还存在分子间π…π相互作用，并导致一维分子柱的形成．二维氢键和一维π…π的协同作用，导致了三维超分子晶体的形成。     

Reactions of 2-pyridylphenylacetonitrile and 1,2-dicyano-1,2-diphenyl-1,2-di(2-pyridyl)ethane with cobalt(II), nickel(II), copper(II) and zinc(II) chlorides and copper(II) bromide

Summary 2-Pyridylphenylacetonitrile (ppa) is oxidized by copper(II) halides in 1,2-dichloroethane to 1,2-dicyano-1,2-diphenyl-1,2-di(2-pyridyl)ethane (dcppe), yielding 41 complexes of dcppe with copper(II) dihalide, [CuX₂(dcppe)₄] (green). Nickel(II) and zinc(II) chlorides react with ppa giving complexes of a general formula [MCl₂(ppa)₂].Dcppe reacts with copper(II), zinc(II) chlorides and copper(II) bromide yielding complexes of formulae [CuCl₂(dcppe)₄] (yellow), [ZnCl₂(dcppe)₂] and [CuBr₂(dcppe)]. No reaction is observed with cobalt(II) and nickel(II) chlorides.     

Two chiral mononuclear and one-dimensional cadmium(II) complexes constructed by (1R,2R)-N1,N2-bis(pyridinylmethyl)cyclohexane-1,2-diamine derivatives: Effect of positional isomerism

Reactions of (1R,2R)-N¹,N²-bis(pyridinylmethyl)cyclohexane-1,2-diamine derivatives, (1R,2R)-2-bpcd and (1R,2R)-3-bpcd [(1R,2R)-2-bpcd = (1R,2R)-N¹,N²-bis(pyridin-2-ylmethyl)cyclohexane-1,2-diamine, (1R,2R)-3-bpcd = (1R,2R)-N¹,N²-bis(pyridin-3-ylmethyl)cyclohexane-1,2-diamine], with CdI₂ in an analogous way led to the formation of a chiral discrete mononuclear complex and a chiral one-dimensional polymeric chain, respectively, which may be attributed to the positional isomerism of the ligands. The chiral organic ligands and complexes display luminescent properties indicating that they may have a potential application as optical materials. Powder second-harmonic generation (SHG) efficiency measurement shows that the SHG efficiency of the complexes is approximately 0.3 and 0.45 times that of KDP, respectively.     

Synthesis,structure and properties of complex compounds of cobalt,nickel, copper and zinc with 2-formylpyridine semicarbazone

2-Formylpyridine semicarbazone L reacts with cobalt, nickel, copper and zinc chlorides, nitrates and perchlorites to form coordination compounds of compositions ML₂X₂·nH₂O (M=Co, Ni, Cu, Zn; X = Cl, NO₃, ClO₄; L = NC₅H₄-CH=N-NH-C(O)-NH₂; n = 0, 1) and CuLX₂·nH₂O (X = Cl, Br, NO₃; n = 0−0.5). Complex CuL(NO₃)₂ has polynuclear, CuLX₂·0.5H₂O (X = Cl, Br), binuclear, and other compounds, mononuclear structures. Azomethine L behaves in them as tridental N,N,O-ligand. Thermolysis of these complexes proceeds through such stages as dehydration (80–95°C), deactivation (145–155°C) and complete theral degradation (170–590°C). Complexes CuLX₂·nH₂O (X = Cl, NO₃; n = 0−0.5) were established to inhibit in vitro the growth and reproduction of 100% of cancer cells of human mieloid leukaemia HL-60 at 10⁻⁴ M concentration. At 10⁻⁵ M concentration they inhibit only 10% of cells, and at 10⁻⁶ M concentration they do not possess anticancer activity.     

Coordination compounds of cobalt(II), nickel(II), and zinc(II) valerates and benzoates with benzohydrazide

Coordination compounds of cobalt(II), nickel(II), and zinc(II) valerates and benzoates with benzohydrazide have been synthesized and characterized by elemental analyses, IR spectra, diffuse reflectance spectra, and thermogravimetric data.     

Synthesis of Ni(II) complexes with chiral derivatives of cyclohexane-1,2-diamine,bycyclo[2.2.2]octane-2,3-diamine,and 1,2-diphenylethane-1,2-diamine

Chiral ligands—derivatives of (1R,2R)-cyclohexane-1,2-diamine, (1R,2R)-diphenylethane-1,2-diamine, and (2S,3S)-bicyclo[2.2.2]octane-2,3-diamine—and octahedral Ni(II) complexes on their basis have been synthesized.     

Complexes of nitrilotrimethylphosphonic acid with cobalt, nickel, copper and zinc

Substances of the types MH₄ntmp, Mg₃[M(Hntmp)]₂, M₂H₂ntmp and Mg[M₂(Hntmp)]₂, where M = Co, Ni, Cu, Zn and H₆ntmp = N[CH₂PO(OH)₂]₃ were prepared. The sodium and cesium salts of the [Co(Hntmp)]³⁻ complexes were also prepared. The IR and electronic spectra and the experimental magnetic susceptibilities indicate that these are high-spin complexes. The coordination surroundings of the central atom consist of a highly distorted octahedron of the ligand oxygen atoms. The nitrogen atom is not coordinated to the central atom.     

Preconcentration of cadmium, cobalt, copper, nickel and zinc by solvent extraction into methyl isobutyl ketone with 1,5-bis [1-(2-pyridyl) ethylidene] thiocarbonohydrazide and 1,5-bis [phenyl-(2-pyridyl) methylene] thiocarbonohydrazide

The synthesis, physicochemical properties and interactions of two new thiocarbohydrazones, namely 1,5-bis[1-(2-pyridyl) ethylidene] thiocarbonohydrazide (APTH) and 1,5-bis[phenyl-(2-pyridyl) methylene] thiocarbonohydrazide (BPTH) have been studied as well as the use of both compounds as extracting reagents. These thiocarbohydrazones form yellow complexes with bivalent metal ions, and these are extractable into methyl isobutyl ketone. Conditions for quantitative extraction of Cd(II), Co(II), Cu(II), Ni(II) and Zn(II) are established from a critical study of the effect of pH, shaking time, reagent concentration in the organic phase, ionic strength and volume ratio of aqueous to organic phase.     

Synthesis and study of copper(II), nickel(II), and cobalt(II) complex compounds with dihydrobenzoxazine derivatives

Complex compounds ML₂ of copper(II), nickel(II), and cobalt(II) with 2-(2-hydroxy-5-nitrophenyl)-4,4-diphenyl-1,4-dihydro-2H-3,1-benzoxazine and 2-(2-hydroxyphenyl)-4,4-diphenyl-1,4-dihydro-2H-3,1-benzoxazine (HL) were prepared by electrochemical and chemical syntheses. The complex formation involves the azomethine form of the ligand and gives a six-membered chelate cycle comprising deprotonated phenol and azomethine groups. The coordination entity has a planar structure with trans arrangement of the nitrogen and oxygen atoms.     

Synthesis,structures and properties of copper(II) and zinc(II) complexes with 1,2-bis(benzimidazol-2-yl)ethane ligands

Transition Metal Chemistry - 1,2-Bis(benzimidazol-2-yl)ethane (bbe) and its transition metal complexes, [Cu(bbe)Cl2]·DMF (1) and [Zn(bbe)Cl2]2(2), have been synthesized and characterized by...     

New copper(II) coordination compounds with 1,3-bis(5-(pyridin-2-yl)-1,2,4-triazol-3-yl)propane

Two new copper(II) complexes with 1,3-bis(5-(pyridin-2-yl)-1,2,4-triazol-3-yl)propane (H₂L), [Cu₂(HL)Cl₃] · H₂O (I) and [Cu(H₂L)](ClO₄)₂ (II), were described. The compounds were characterized by elemental analysis, IR spectroscopy, and magnetochemical data. According to X-ray diffraction data (CIF files CCDC nos. 1497511 (I), 1497512 (II)), complex I is binuclear and the metal cations are bound by the nitrogen atoms of the triazole ring and by the chloride anion. Complex II is mononuclear. Analysis of the temperature dependence of the magnetic susceptibility of I attests to the antiferromagnetic coupling of paramagnetic centers (–2J = 18 cm^–1). Exchange channels are analyzed by means of density functional theory (B3LYP/6-311G(d)) using the broken symmetry approach.     

Acetylsalicylhydroxamic acid and its cobalt(II), nickel(II), copper(II) and zinc(II) complexes

Acetylsalicylhydroxamic acid (AcSHA) was prepared and characterized. Its pK_a value was determined as 7.78. Solid metal complexes of AcSHA were also prepared and characterized by elemental analysis, electronic and i.r. spectroscopies, and by magnetic moment measurements. The shift of both hydroxamic and acetyl carbonyl vibrations to lower frequencies clearly indicates that AcSHA is bonded through oxygen atoms to the metal ions as a tridentate ligand. On the basis of the experimental data, structures for the complexes are purposed.     

Synthesis,spectroscopy and thermal analysis of nickel(II), palladium(II) and copper(II) complexes with N,N′-bis(2-hydroxyethyl)-oxamide

Summary The new complexes K₂[Ni(H₂heo)₂]·3H₂O, K₂[Pd-(H₂heo)₂], K₂[Cu(heo)]·3H₂O and [Cu₂(heo)·2H₂O] {heo = [(CONCH₂CH₂O)₂]^4-} were prepared and characterized by chemical analyses, conductivity measurements, thermogravimetry, magnetic susceptibility and i.r. and u.v. spectroscopy.Monomeric square planar structures with MN₄ coordination spheres are found for the nickel and palladium complex anions.For copper, two different complexes were identified. In slightly alkaline media, a green insoluble nonelectrolyte [Cu₂(heo)·2H₂O] was prepared; the two copper(II) centres are bridged by the tetra-deprotonated ligand in a trans-planar configuration with the H₂O molecules strongly coordinated to the copper(II). The copper(II) monomer has been prepared in strong alkaline media, this anion also contains the tetra-deprotonated ligand in a planar trans form.     

Chiral compounds with two hypervalent silicon atoms-Si,Si'-disubstituted bls(O-Si) chelate derivatives of 1,2-bis(dimethylsilylmethyl)-1,2-diacetylhydrazine

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, p. 492, February, 1989.     

Molten potassium thiocyanate: The reactions of some compounds of iron,cobalt, nickel,copper and zinc

The electronic spectra of four transition metal cations stable in molten potassium thiocyanate [Fe(II), Co(II), Ni(II) and Cu(I)] are reported together with their reactions and those of three unstable cations [Fe(III), Co(III) and Cu(II)] with a variety of anions including cyanide, cyanate and sulphide. A novel reduction of zinc(II) sulphate is also reported.