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.     

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.     

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…     

Complexes of N-aroyl-N′-thiobenzohydrazide with cobalt(II), nickel(II) and zinc(II)

Summary New potential tetradentate ligands, N-benzoyl-N-thiobenzohydrazide (H₂BTBH) and N-salicyl-N-thiobenzohydrazide (H₂SBTH) have been prepared and characterized. Their complexes with Co^II, Ni^II and Zn^II have been prepared and characterized on the basis of elemental analyses, magnetic susceptibility measurements, and u.v.-vis., i.r. and ¹H-n.m.r. spectral studies. The bonding and stereochemistries of the complexes are discussed. H₂BTBH, H₂SBTH and the complexes have been screened towards a number of bacteria.     

Copper(II)–8-mercaptoquinoline,copper(II)–5,8-dimercaptoquinoline and copper(II)–5-thiomethyl-8-mercaptoquinoline complexing in a copper(II)hexacyanoferrate(II) gelatin-immobilized matrix

Novel complexing processes in the Cu^II–8-mercaptoquinoline, Cu^II–5,8-dimercaptoquinoline and Cu^II–5-thiomethyl-8-mercaptoquinoline systems proceeding in the copper(II)hexacyanoferrate(II) gelatin-immobilized matrix in contact with aqueous solutions of the ligands indicated, have been studied. Under the conditions specified for complexing in the Cu^II–8-mercaptoquinoline system, only a monomeric water-insoluble coordination compound was formed. In the Cu^II–5,8-dimercaptoquinoline system, three coordination compounds were formed and, in the Cu^II–5-thiomethyl-8-mercaptoquinoline system, two such compounds were formed. Conversely, complexing in solution or solid phase results in the formation only coordination compounds in each of the system studied.     

Palladium(II) and platinum(II)-C(3)-substituted 2,2′-bipyridines

Reaction of Pd(OAc)₂ with HL¹ and HL² (HL¹=6-iso-propyl-2,2-bipyridine; HL²=6-neo-pentyl-2,2-bipyridine), followed by treatment with LiCl or KI, gives [PdCl(L¹)]₂, (1), [PdCl(L²)]₂ (2), and [PdI(L²)]₂ (3), respectively. The chloride bridge in complexes1 and2 is split by PPh³ to give the mononuclear species PdCl(L¹)(PPh₃) (4) and PdCl(L²)(PPh₃) (5). Spectroscopic data provide evidence for coordination of the deprotonated ligands through a nitrogen and the C₍₃₎ atom of the 6-substituted pyridine. An analogous platinum complex PtCl(L³)(SMe₂) (6) (HL³=6-tert-butyl-2,2-bipyridine) was obtained from trans-PtClMe(SMe₂)₂ and HL³. The crystal structures of compounds1 and6 have been solved by X-ray diffraction analysis.Dipartimento di Chimica, Universita di Sassari, via Vienna 2, I-07100 Sassari, Italy; Dipartimento di Chimica Strutturale e Stereochimica Inorganica, Universita di Milano, Centro CNR, I-20133 Milano, Italy; Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1127–1137, August, 1999.     

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).     

Copper(II), zinc(II) and mixed metal copper(II)-zinc(II) peroxocomplexes containing 2,2′,6′,2″-terpyridine

Summary Facile reaction of 2,2,6,2-terpyridine (L; terpy) with copper or zinc powders or their mixtures, in the presence of an excess of H₂O₂, leads to novel complexes [Cu(L)-(O₂ ^2–)]·3H₂O, [Zn(L)(O ₂ ^2– )]·H₂O and [Cu,Zn(L)₂(O ₂ ^2– )₂]· 4H₂O, respectively, which were isolated and characterized by elemental and micro- analysis, e.s.r., electronic, i.r. and thermogravimetric analysis in air and argon.     

甲壳胺与铜(II)、镍(II)、锌(II)配合物的合成及性质

甲壳胺（Ｃｈｉｔｏｓａｎ,简写为ＣＴＳ）是甲壳素脱乙酰基的产物,是一种线性半刚性高分子,由于ＣＴＳ分子中有—ＮＨ２、—ＯＨ和—ＮＨＣＯＣＨ３,故它对过渡金属具有很强的螯合能力,因而在废水处理中重金属的回收方面得到了广泛应用［１］。同时ＣＴＳ与过渡金属和稀土金属形成的配合物还具有模拟酶的功能,故有关配合物在催化加氢［２］和高分子的聚合反应［３］等方面的研究日趋活跃。然而,有关ＣＴＳ与过渡金属离子配合物的固态组成研究尚无文献报道。ＣＴＳ与过渡金属离子的配合物大多是以固液反应来制备的［４,５］。本文在…     

邻苯二酚-3,6-二甲撑亚氨基二乙酸的酸离解平衡及其与碱土金属、锰(II)、镉(II)、锌(II)、钴(II)、镍(II)、铜(II)、铁(II)、钍(IV)及铀酰离子配合物稳定性的研究

本文报道用PH滴定法测得KNO3水溶液中邻苯二酚-3,6-二甲撑亚氨基二乙酸(CBMIDA, H6L)的六级酸解离常数及CBMIDA的镁(II)、钙(II)、锶(II)、钡(II)、镍(II)、锌(II)、钴(II)、镉(II)、锰(II)、铜(II)、铁(II)、钍(IV)和铀酰离子的配合物稳定常数及配合物的质子化常数. 讨论了CBMIDA的逐级酸离解的动态平衡机理以及金属离子与CBMIDA形成的各种配合物的配位形式.     

2,4′-Bipyridyl complexes with cobalt(II) and nickel(II)

Summary Complexes of empirical formulae [ML₂Cl₂(OH₂)₂], [CoL₂Br₂(OH₂)₂]L·4H₂O, [NiL₂Br₂(OH₂)₂]L₂·2H₂O, [ML₂(OH₂)₄]L₂(NO₃)₂ and [ML₄(OH₂)₂](ClO₄)₂·2H₂O (M = Co^II, Ni^II, L = 2,4-bipyridyl) were synthesized and characterized by elemental and spectral analyses. The thermal decomposition of the complexes was also investigated.Author to whom all correspondence should be directed.     

Mn(II)-Fe(II)-MCF的制备及催化性能

以改性玉米苞叶纤维为载体(MCF),负载Mn(II)和Fe(II)制备了Mn(II)-Fe(II)-MCF复合材料,催化H₂O₂氧化水中染料。通过傅立叶变换红外/近红外成像系统和扫描电子显微镜对其结构和形貌进行表征。实验结果表明:当染料浓度为10 mg·L^-1,Mn(II)-Fe(II)-MCF用量为4 g·L^-1,H₂O₂初始浓度为1.56 mmol·L^-1,Mn(II)-Fe(II)-MCF对四种染料的催化效率明显不同。阳离子蓝X-GRRL(CBX-GRRL)降解效果最好,其次是甲基橙(MO)、次甲基蓝(MB)和罗丹明B(RhB)。对染料的氧化反应进行动力学分析,MO的降解反应为二级反应,CBX-GRRL、MB和RhB的降解反应均为一级反应。Mn(II)-Fe(II)-MCF适合催化氧化偶氮染料废水。     

4,4′-Bipyridine complexes of molybdenum(II) and tungsten(II)

Treatment of [MI₂(CO)₃(NCMe)₂] with two equivalents of 4,4-bipyridine (4,4-bipy) in CH₂Cl₂ at room temperature gave the MeCN displaced products, [MI₂(CO)₃(4,4-bipy-N)₂] (1) and (2). Equimolar amounts of [MI₂(CO)₃(NCMe)₂] and L (L = PPh₃, AsPh₃ or SbPh₃) react to give [MI₂(CO)₃(NCMe)L], which when reacted in situ with 4,4-bipy yield the new complexes, [MI₂(CO)₃(4,4-bipy-N)L] (3)–(8). Reaction of equimolar quantities of [WI₂(CO)(NCMe)( ²-RC₂R)₂] (R = Me or Ph) and 4,4-bipy gave the new bis(alkyne) complexes, [WI₂(CO)(4,4-bipy-N)( ²-RC₂R)₂] (9) and (10). Treatment of [MI₂(CO)₃(NCMe)₂] with two equivalents of (9) or (10) in CH₂Cl₂ at room temperature affords the bimetallic complexes, [MI₂(CO)₃{WI₂(CO)(4,4-bipy-N,N)( ²-RC₂R)₂}₂] (11)–(14). Equimolar quantities of [MI₂(CO)₃(NCMe)(PPh₃)] (prepared in situ) and (9) or (10), react to give the 4,4-bipy-bridged complexes, [MI₂(CO)₃{WI₂(CO)(4,4-bipy-N,N)( ²-RC₂R)₂}(PPh₃)] (15)–(18). All the new complexes, (1)–(18) were characterised by elemental analysis (C, H and N), i.r. and ¹H-n.m.r. spectroscopy.     

NICKEL(II) AND ZINC(II) COMPLEXES OF β-ALANINEHYDROXAMIC ACID

Abstract

Potentiometric and spectrophotometric studies of Ni(II) coordination to β-alaninehydroxamix acid (β-Alaha) have shown 4N coordination of β-Alaha for 1:2 species and their planar geometry. The geometry of the species formed in the nickel(II)-β-Alaha below ca. pH 7 is octahedral. The differences between the stabilities of zinc(II)-β-Alaha and zinc(II)-α-alaninehydroxamic acid complexes can be explained by the terdentate coordination of the β-alaninehydroxamic acid.     

Copper(II), nickel(II), cobalt(II) and oxovanadium(IV) complexes of substituted β-hydroxyiminoanilides

Complexes of the general formula, ML₂ [M = Cu^II, Ni^II, Co^II and OV^IV; L = 1,2,3,5,6,7,8,8a-octahydro-3-hydroxyimino-N-(4-X-phenyl)-l-phenyl-5-(phenylmethylene)-2-naphthalenecarboxamide (X = H, Me, OMe, Cl)] have been prepared and characterized on the basis of elemental analysis, magnetic moments and i.r., e.p.r. and electronic spectra. These metal complexes contain the N₄ chromophore with the ligand coordinating through nitrogens of the azomethine and deprotonated anilide functions. C.v. measurements indicate that the copper(II) complexes are quasi-reversible in acetonitrile solution. Square planar and square pyramidal structures are assigned respectively to the copper(II) and oxovanadium(IV) complexes, whereas tetrahedral geometry is assigned to the nickel(II) and cobalt(II) complexes. Deprotonated anilide nitrogen is involved in coordination and the presence of an electron-donating group para to the anilide function decreases the ΔE values of the d–d transitions while the value is found to increase when electron-withdrawing groups are substituted. Line spacing in the e.p.r. spectra of the copper(II) and oxovanadium(IV) complexes increases when methyl group is para to the anilide group, and decreases when this group is replaced by methoxy or chloro. The ν(C–N) of the anilide group and the ν(C-N) of the azomethine function of the oxime metal complexes are metal-sensitive and the blue shift for the above stretching frequencies follows the order: copper(II) > oxovanadium(IV) > nickel(II) ≈ cobalt(II). This revised version was published online in June 2006 with corrections to the Cover Date.     

超临界二氧化碳中卟啉与钴(II)、镍(II)、锌(II)配合物反应动力学

用紫外-可见光谱研究了钴(II)、镍(II)、锌(II)的1, 1, 1, 5, 5, 5-六氟-2, 4-戊二酮-二水配合物[M(hfac)2(H₂O)₂, M=Co、Ni、Zn]与5, 10, 15, 20-四(五氟苯基)卟啉[H2tpfpp]在超临界二氧化碳中反应生成金属卟啉[M(tpfpp)]的反应动力学. 在金属配合物大大过量时, 反应对卟啉为一级. 其表观一级速率常数随钴(II)、镍(II)配合物的浓度增加先增加、而后趋于稳定, 而表观一级速率常数随锌(II)配合物的浓度增加线形增加. 根据实验事实, 讨论了反应的机理, 得到了相应的热力学和动力学参数.     

Synthesis,crystal structure,thermal decomposition,and XPS studies of homo and heterotrinuclear Cu(II)–Cu(II)–Cu(II) and Cu(II)–Ni(II)–Cu(II) complexes obtained from salpn type ligands

In this study, a mononuclear CuL complex was prepared by the use of bis-N,N′-(salicylidene)-1, 3-propanediamine (LH₂) and Cu²⁺ ion. NiCl₂ and NiBr₂ salt were treated with this complex in dioxanewater medium and two new complexes [(CuL)₂NiCl₂(H₂O)₂] and [(CuL)₂NiBr₂(H₂O)₂)] with Cu(II)–Ni(II)–Cu(II) nucleus structure were obtained. In addition to this bis-N,N′-(2-hydroxybenzyl)-1,3-diaminopropane (L^HH₂) was prepared by the reduction of LH₂ with NaBH₄ in MeOH medium. The treatment of this reduced complex with Cu²⁺ ion resulted a complex [(CuL^H)₂CuCl₂] with a structure of Cu(II)–Cu(II)–Cu(II). The complexes prepared were characterized by the use of elemental analysis, IR spectroscopy, thermogravimetric and X-ray diffraction methods. The crystal structures of [(CuL)₂NiBr₂(H₂O)₂] (СIF file CCDC 1448402) and [(CuL^H)₂CuCl₂] (СIF file CCDC 1448401) complexes were elucidated. It was found that halogen ions are coordinated to terminal Cu²⁺ ions which are in a distorted square pyramid coordination sphere. It was determined that the central Cu(II), which joins terminal square pyramidal Cu(II), was coordinated only by the phenolic oxygens of the ligand while the central Ni(II) was coordinated by two phenolic oxygens of the organic ligand and two water molecules. These complexes were investigated by XPS and it was found that the terminal and central Cu²⁺ ions were different in Cu(II)–Cu(II)–Cu(II) complex. Also, the thermal degradation of the CuLH complex unit was observed to exothermic in contrast to the expectations.