Copper(II)–1,2-bis(thiocarbamoyl)hydrazine and copper(II)–(1-carbamoyl-2-thiocarbamoyl)hydrazine complexing in copper(II)hexacyanoferrate(II) gelatin-immobilized matrix systems

The complex formation that occurs in gelatin-immobilized copper(II)hexacyanoferrate(II) matrices upon contact with aqueous alkaline (pH 12.0) solutions of 1,2-bis(thiocarbamoyl)hydrazine, H₂NC(S)NHNHC(S)NH₂ and 1-carbamoyl-2-(thiocarbamoyl)hydrazine, H₂NC(O)NHNHC(S)NH₂ has been studied. The reaction of each of these ligands with copper(II) is preceded by the destruction of copper(II)hexacyanoferrate(II) in an alkaline medium to form a polymeric copper(II) hydroxide, which is involved in the subsequent copper(II)–ligand complex formation. In both Cu^II–N ligand systems, two complex compounds are formed; the water-insoluble Cu₂B₂(H₂O)₂ dimer and a water-soluble product of tentative composition [CuB(HB)]^– (H₂B=ligand).     

EPR on bis(1,2-dithiosquarato)cuprate(II) in the bis(1,2-dithiosquarato)nickelate(II) host lattice — structure and spectroscopy‡

EPR spectroscopy is a well suited analytical tool to monitor the electronic situation around paramagnetic metal centres as copper(II) and therefore the structural influences on the paramagnetic ion. 1,2-Dithiosquaratometalates are available by direct synthesis from metal salts with dipotassium-1,2-dithiosquarate and the appropriate counter cations. Synthesis and characterisation of bis(benzyltributylammonium)1,2-dithiosquaratonickelate(II), (BzlBu₃N)₂[Ni(dtsq)₂], and bis(benzyltributylammonium)1,2-dithiosquaratocuprate(II), (BzlBu₃N)₂[Cu(dtsq)₂], with benzyltributylammonium as the counter ion is reported and the X-ray structures of two complexes, (BzlBu₃N)₂[Ni(dtsq)₂] and (BzlBu₃N)₂[Cu(dtsq)₂], are presented. Both complexes, crystallising in the monoclinic space group P2₁/c, are isostructural with only small differences in the coordination sphere due to the different metal ions. The diamagnetic nickel complex is therefore well suited as a host lattice for the paramagnetic Cu(II) complex to measure EPR for additional structural information.     

Synthesis and magnetic properties of copper(II)-cobalt(II) complexes ofN,N′-1,2-propanedisalicylamidatocuprate(II)

Summary The binuclear metal complexes [Cu(sampn)Co(L)₂] (L=bipy, phen), have been prepared by the reaction of sodiumN,N-1,2-propanedisalicylamidatocuprate(II) heptahydrate, Na₂[Cu(sampn)] 7H₂O, with a divalent metalion, and 2,2-bipyridine or 1, 10-phenathroline. The complexes were characterized by variable-temperature magnetic susceptibility measurements; the results indicate that a weak antiferromagnetic spin-exchange interaction operates between the metal ions.     

Crystal structures ofcatena-[diligatocadmium(II) tetra-μ-cyanocadmate(II)] host clathrates: Diamminecadmium(II) tetracyanocadmate(II)-benzene(1/2), diamminecadmium(II) tetracyanocadmate(II)-aniline(1/2), ethylenediaminecadmium(II) tetracyanocadmate(II)-aniline(1/2), and a novel type bis(aniline)cadmium(II) tetracyanocadmate(II)-aniline(2/1)

The crystal structures of the four title clathrate compounds Cd(NH₃)₂Cd(CN)₄ · 2C₆H₆,I, Cd(NH₃)₂Cd(CN)₄ · 2C₆H₅NH₂,II, Cd(NH₂CH₂CH₂NH₂)Cd(CN)₄ · 2 C₆H₅NH₂,III, and Cd(C₆H₅NH₂)₂Cd(CN)₄ · 0.5C₆H₅NH₂,IV, have been analyzed by single crystal X-ray diffraction methods. CompoundI crystallizes in the monoclinic space groupC2/c,a = 12.063(2),b = 12.174(2),c = 14.621(1) Å,β = 90.976(9)°,Z = 4,R = 0.042 for 2388 reflections;II: monoclinic C₂/c,a = 12.1951(9),b = 12.078(1),c = 14.6921(7) Å,β = 93.436(5)°,Z = 4,R = 0.039 for 2374 reflections;III: monoclinicCc,a = 11.027(1),b = 12.0767(9),c = 15.837(1) Å,β = 92.059(9)°,Z = 4,R = 0.041 for 2883 reflections; andIV: monoclinicP2₁/n,a = 15.169(2),b = 16.019(2),c = 8.866(1) Å,β = 95.73(1)°,Z = 4,R = 0.052 for 3612 reflections. The three-dimensionalcatena-[diamminecadmium(II) tetra-μ-cyanocadmate(II)] hosts ofI andII are substantially isostructural to that of the already known Hofmann-Td-type Cd(NH₃)₂Hg(CN)₄ · 2C₆H₆. The three-dimensional en-Td-typecatena-[catena-μ-ethylenediaminecadmium(II) tetra-μ-cyanocadmate(II)] host ofIII, reinforced by the catena-μ-en linking between the octahedral Cd atoms, accommodates the aniline as the guest with a monoclinic distortion from the tetragonal symmetry of the previously reported en-Td-type benzene clathrate. InIV dual behavior of aniline, one as the unidentate ligand in the three-dimensional host and the other as the guest in the cage-like cavity, has been demonstrated.     

Synthesis and spectroscopic studies of new Cu(II), Ni(II), VO(IV) and Zn(II) complexes with N,N′-bis(2-hydroxynaphthalin-1-carbaldehydene)-1,2-bis-(o-aminophenoxy)ethane

A novel tetradentate, N₂O₂-type Schiff base, synthesized from 1,2-bis-(o-aminophenoxy)ethane and 2-hydroxynaphthalin-1-carbaldehyde, forms stable complexes with transition metal ions such as Cu(II), Ni(II), VO(IV) and Zn(II) in DMF. Microanalytical data, elemental analyses, magnetic measurements, ¹H NMR, UV, visible and IR-spectra as well as conductance measurements were used to confirm the structures.     

Mukaiyama Aldol Reaction of 1,2-Bis(trimethylsiloxy) Cyclobutene Catalyzed by Magnesium(II) Iodide

Theuniquereactivityof1,2-bis(trimethylsiloxy)cyclobutene(BTCB)towardscarbonylsubstrateoritsacetalequivalentunderLewisacidcatalysiswasfirstrecognizedbyKuwajimaandNakamurain19771.Thereactiongenerallyledtothegeminalacylationorreductivesuccinoylationofcarbonylsubstrateviatheacid-catalyzedpinacol-typerearrangement(acylmigration)oftheMukaiyamaaldoladductasillustratedinEq.12.OR1R2R1R2OROROR1R2OOR=TMSCO2HOR1R2L.A.acidor(1)OTMSOTMS+Furtherdevelopmentofthisreactionhasbeencarriedoutexten…     

Complex Species in Aqueous Solutions of 4-Chloro-1,2-Phenylenediamine-N,N,N′,N,'-Tetraacetic Acid with Magnesium(II), Calcium(II), Strontium(II), Barium(II), Zinc(II) and Cadmium(II)

Abstract

The coordination in aqueous solution of 4-chloro-1,2-phenylenediamine-N',N',N',N'-tetraacetic acid (4-Cl-o-PDTA) with Be(II) and with the transition metal cations cobalt(II), nickel(II) and copper(II) was reported in earlier publications.^1,2 In this note a study is presented of the coordination in aqueous solution (25°C, 1 = 0.1 M in KC1) of 4-CI-o-PDTA acid with magnesium(II), calcium(II), strontium(II), barium(II), zinc(II) and cadmium(II).     

Synthesis and characterization of binuclear μ-oxalato nickel(II), copper(II) and zinc(II) complexes with 3,3′-diamino-N-methyl-dipropylamine or trans-1,2-diaminocyclohexane

New binuclear complexes of the type [(Ni(Medpt)NO₃)₂ox] (1) (Medpt=3,3′-diamino-N-methyl-dipropylamine, H₂ox=oxalic acid), [(Ni(dach)₂)₂ox]NO₃·2H₂O (2) (dach=trans-1,2-diaminocyclohexane), [(Cu(Medpt))₂ox]X₂·yH₂O (X=NO₃, y=2 2/3 (3); X=ClO₄, y=0 (4)) and [(Zn(dach)₂)₂ox](ClO₄)₂·2H₂O (5) have been prepared and characterized by IR and UV–Vis spectroscopies. Spectroscopic data are consistent with oxalate-bridged structures between six-coordinated (N₃O₃ or N₄O₂) Ni(II) (compounds 1 or 2), five-coordinated (N₃O₂) Cu(II) (compounds 3 and 4) or six-coordinated (N₄O₂) Zn(II) (compound 5). The crystal structure of [(Cu(Medpt))₂ox](NO₃)₂·2 2/3 H₂O (3) has been determined by single-crystal X-ray analysis. The structure of (3) consists of centrosymmetric binuclear cations [(Medpt)Cu(ox)Cu(Medpt)]²⁺, nitrate anions and water molecules of crystallization. The copper atom is five-coordinated by two oxalate–oxygen and three Medpt–nitrogen atoms, in a hybrid arrangement between trigonal–bipyramidal and square–pyramidal. The temperature dependence of magnetic susceptibility (1.8–300 K) was measured for compounds 1–4. Magnetochemical measurements show that Ni(II) complexes are antiferromagnetically coupled, J=−29.4 (1) and −32.7 cm⁻¹ (2) (H=−JS₁S₂) while the Cu(II) complexes present a very weak coupling, J=−2.6 (3) and +1.9 cm⁻¹ (4), being antiferro- and ferromagnetic in nature.     

N,N'-1,2-丙二水杨酰胺合铜(II)酸根的双核Cu(II)-Ni(II)配合物的合成和磁性

本文合成了两个新的双核配合物, [Cu(sampu)Ni(L)2], sampn^4^-表示N,N'-1,2-丙二水杨酰胺阴离子, L表示2,2-联吡啶(bpy)或1,10-菲咯啉(phen),经元素分析, IR和电子光谱等方法已推定配合物具有酚氧桥结构和Cu(II)及Ni(II)的配位环境分别为平面四方及八面体构型, 配合物的变温磁化率已测(4-300K), 其数值用最小二乘法和从自旋哈密顿算符H=-2JS1S2导出的磁方程拟合, 求得交换参数为J=-1.90cm^-^1(pby)和J=1.68cm^-^1(phen), 表明两个Cu(II)-Ni(II)双核配合物中有弱的反铁磁自旋交换相互作用。     

N,N'-1,2-丙二水杨酰胺合铜(II)酸根的双核Cu(II)-Ni(II)配合物的合成和磁性

本文合成了两个新的双核配合物, [Cu(sampu)Ni(L)2], sampn^4^-表示N,N'-1,2-丙二水杨酰胺阴离子, L表示2,2-联吡啶(bpy)或1,10-菲咯啉(phen),经元素分析, IR和电子光谱等方法已推定配合物具有酚氧桥结构和Cu(II)及Ni(II)的配位环境分别为平面四方及八面体构型, 配合物的变温磁化率已测(4-300K), 其数值用最小二乘法和从自旋哈密顿算符H=-2JS1S2导出的磁方程拟合, 求得交换参数为J=-1.90cm^-^1(pby)和J=1.68cm^-^1(phen), 表明两个Cu(II)-Ni(II)双核配合物中有弱的反铁磁自旋交换相互作用。     

Spectroscopy and stereochemistry of the optically active copper(II), cobalt(II) and nickel(II) complexes with Schiff bases N,N′-(1R,2R)-(−)-1,2-cyclohexylenebis(3-methylbenzylideneiminato) and N,N′-(1R,2R)-(−)-1,2-cyclohexylenebis(5-methylbenzylideneiminato)

Schiff bases obtained from N,N′-(1R,2R)-1,2-cyclohexanediamine and 2-hydroxy-3-methylbenzaldehyde, 2-hydroxy-5-methylbenzaldehyde, have been used as ligands for copper(II), cobalt(II) and nickel(II). The complexes were characterized with UV–Vis, circular dichroism (CD), infrared, diamagnetic and paramagnetic ¹H NMR spectroscopy. CD spectra revealed exciton coupled π→π* transitions. Assignments of LMCT and d–d transitions in CD spectra of Ni(II), Co(II) and Cu(II) complexes is proposed. CD data are characteristic for central ion tetrahedral distortion from the planarity and λ conformation of the cyclohexane ring. ¹H NMR of Ni(II) complexes exhibited significant coordination shifts of CHN and ring protons which are in the closest proximity to Ni(II). The ¹H NMR paramagnetic spectra of Co(II) complexes revealed the most upfield shifted resonance at −60 ppm assigned to CHN and −28 ppm to hydrogen atom at C(5′) of the phenyl ring. Results of spectral analyses suggest central ions in a distorted square-planar geometry with N₂O₂ chromofore group.     

One Dimensional Coordination Polymer Constructed by 1,2-Bis(4-pyridinecarboxamido)ethane and Copper(II)

IntroductionInrecentyears ,thesynthesisandcharacterizationofco ordinationpolymershavebeenrapidlyexpandingowingtoafundamentalinterestintheirfascinatingstructuraldiversityandpotentialapplicationsasfunctionalmaterials .1 4 Thesyn thesisofcoordinationpolymerswith 4 ,4′ bipyridine (4 ,4′ bipy)orrelatedspeciesasbifunctionalligandandmetalionhasgeneratedaconsiderablenumberofnoveltopologicalframeworks ,suchasT shaped ,5ladder,6 brickwall,7squareorrectangulargrid8,9andotheruncommonmotifs .Herewereport…     

Synthesis and spectral studies of Cu(II), Ni(II), Co(II) macrocyclic complexes by template reaction of (±)- trans -1,2-diaminocyclohexane,metal(II) nitrate and salicylaldehyde derivatives

Six new macrocyclic complexes were synthesized by template reactions of salicylaldehyde derivatives with (±)-trans-1,2-diaminocyclohexane and metal(II) nitrates. The metal to ligand ratio was 1 : 1. The Cu(II) complexes are proposed to be square planar and the Ni(II) and Co(II) complexes are proposed to be tetrahedral. The complexes are 1 : 2 electrolytes as shown by their molar conductivities (Λ_M) in DMF. The metal complexes are characterized by elemental analyses, FT-IR, UV–Vis, magnetic susceptibility measurements, molar conductivity measurements and mass spectra.     

BINDING ABILITY OF OXINE-LIKE LIGANDS. POTENTIOMETRIC AND POLAROGRAPHIC STUDY ON Ni(II), Co(II), Zn(II) AND Cd(II) COMPLEXES OF 9-HYDROXYPYRIDO(1,2,-α)PYRIMIDIN-4-ONE

Abstract

Potentiometric and polarographic studies of metal ion coordination with 9-hydroxypyrido[1,2-α]pyrimidin-4-one (HPP) with Ni(II), Zn(II), Co(II) and Cd(II) ions have been carried out. For comparison, stability constants with 8-hydroxy-imidazo[1,2-α]pyridine (HIP) were also measured. Due to the low solubility of the latter ligand complexes, measurements were made also in dioxan/water solutions. In the case of both ligands the coordination mode is the same. The oxine-like binding via {N, O^?} donor set leads to formation of stable ML and ML₂ complexes. Stability constants clearly indicate that both ligands are very effective and the HPP, having a more favourable position of the electron pair on nitrogen, forms stronger complexes with smaller metal ions i.e., Ni(II), Zn(II) and Co(II). Cd(II) is better fitted to the HIP donor set.     

PH电位法研究水杨醛缩氨基硫脲与铜(II)、锌(II)、镍(II)、钴(II)、锰(II)及镉(II)的相互作用

本文为了进一步了解具有生物活性的木杨醛缩氨基硫脲在溶液中与常见金属离子的作用本质, 在半微量恒温滴定池上用PH电位法研究了该物质与铜(II)、锌(II)、镍(II)、钴(II)、锰(II)及镉(II)等二价金属离子的配位作用.     

β-diketone complexes of manganese(II), cobalt(II), nickel(II) and palladium(II)

Summary The reactions of manganese(II), cobalt(II) and nickel(II) acetates (1 mole) with antipyrine-4-azo--ethylcyanoacetate (HL¹) and antipyrine-4-azo--acetylacetone (HL²) (1 mole) produce complexes of the M(L)₂ type. K₂PdCl₄ (1 mole) reacts with HL¹ and HL² (1 mole) to yield complexes of the general formula PdLCl, the ligands behaving as monobasic tridentates. The electronic spectral and magnetic data show the complexes to be high-spin octahedral, whereas the palladium(II) complexes are diamagnetic square planar. The complexes were characterized by elemental analyses, conductance measurements and i.r. and electronic spectra as well as magnetic susceptibility measurements and thermal (t.g.a. and d.t.a.) analysis.Nuclear Material Authority.     

PH电位法研究水杨醛缩氨基硫脲与铜(II)、锌(II)、镍(II)、钴(II)、锰(II)及镉(II)的相互作用

本文为了进一步了解具有生物活性的木杨醛缩氨基硫脲在溶液中与常见金属离子的作用本质, 在半微量恒温滴定池上用PH电位法研究了该物质与铜(II)、锌(II)、镍(II)、钴(II)、锰(II)及镉(II)等二价金属离子的配位作用.     

[Ethylene-1,2-bis(diphenylphosphine)-P,P′]dinitratoplatinum(II) and cis-bis[(diphenylphosphinomethyl)diphenylphosphine oxide-O,P]platinum(II) dinitrate dihydrate

In [Pt(dppe)(NO₃)₂], where dppe is ethyl­ene-1,2-bis­(di­phenyl­phosphine) (C₂₆H₂₄P₂), the Pt atom is coordinated by the two P atoms and by two O atoms of the two nitrate ions. The mol­ecule has a distorted square-planar geometry, with one of the nitrate groups directed on each side of the plane. The cation in cis-[Pt(dppmO-O,P)₂](NO₃)₂·2H₂O, where dppmO is bis­(di­phenyl­phosphino­methyl)­di­phenyl­phosphine oxide (C₂₅H₂₂OP₂), comprises two five-membered chelate rings, each dppmO ligand being coordinated to platinum through one P atom and the O atom. The larger P—Pt—P angle of 102.25 (4)° is due to steric interactions between the two phenyl groups on each P atom.     

1,2-二（二苯基膦）乙烷氯化钯(II)的合成及催化活性

以卤化钯（X=Cl、 Br、 I）为原料,乙腈为溶剂,与1,2-二（二苯基膦）乙烷反应,合成了1,2-二（二苯基膦）乙烷卤化钯[Pd(dppe)X₂, dppe=1,2-二（二苯基膦）乙烷],产率均高于96％,其结构经¹H NMR, XRD和元素分析确证。以Suzuki反应和Stille C—C偶联反应为模板反应,研究了Pd(dppe)Cl₂的催化活性。结果表明：Pd(dppe)Cl₂对2-氯噻吩和对甲氧基苯硼酸的Suzuki偶联反应、4,7-二氯苯并噻二唑核或其他含苯并噻二唑核的卤代芳烃与其他芳香核的锡试剂的Stille C—C偶联反应的催化转化率分别为80%~85%和52%~60%,催化活性优于四（三苯基膦）钯(70%~85%和43%~50%)。     

Metallothionein Induction by Cd(II) and Zn(II)

Blood may contain high proportion of the toxic and essential metals.Blood is responsiblefor the transport of ion of such metals.The organs such as the kidney,liver and placentaare exposed to a large proportion of the metals which enter the blood and may b…