STUDIES ON THE BACTERIAL ACTIVITY OF COBALT(III) COMPLEXES. PART III. COBALT(III) CARBOXYLATE COMPLEXES

Abstract

Cobalt(III) complexes of the type [Co(en)₂(chel)]X.nH₂O where en = ethylenediamine, chel = phthalato = C₆H₄CO₂)^2? ₂, maleato = (O₂CCH = CHCO₂)^2?, succinato = (O₂CCH₂CH₂CO₂)^2?, homophthalato = (O₂CC₆H₄(CH₂)CO₂)^2?, citraconato = (O₂CC(CH₃) = CHCO₂)^2?, itaconato = (CH₂ = C(CO₂)CH₂CO₂)^2?, X = NO^? ₃, Br^?, (O₂CC₆H₄CO₂H)^?, (O₂CHC = CHCO₂H)^?, (O₂C(CH₂)₂CO₂H)^?, (O₂CC₆H₄(CH₂)CO₂H)^?, (O₂CHC = C(CH₂)-CO₂H)^?, and (O₂C-CH₂?C(= CH₂)-CO₂H)^?, [Co(en)₂(malonato)]X.2H₂O (where malonato = (O₂CCH₂CO₂)^2?, X = Cl^?, Br^?, and NO^? ₃) and [Co(en)₂CO₃]Cl.2H₂O have been investigated for their bacterial activity against Escherichia coli B growing on EMB agar and in minimal glucose media both in lag and log phases. Among the most active are where chel = phthalato and homophthalato. The effects are distinct from those known for compounds of Pt, e.g., cis?[Pt(NH₃)₂Cl₂] and rhodium, e.g., trans?[Rh(C₅H₅N)₄,Cl₂].6H₂O. Antagonisms are reported.     

1,1—二氰乙烯基—2,2—二硫醇盐第一过渡系列金属配合物的研究 Ⅱ.钒(Ⅳ)和铁(Ⅲ)配合物的研究

文献中研究了1,1-二氰乙烯基-2,2-二硫醇盐(简称i-mnt)的Cu(Ⅱ)和 Ni(Ⅱ)配合物.现合成出i-mnt的钒(Ⅳ)和铁(Ⅲ)配合物,根据钒(Ⅳ)配合物的ESR谱和铁(Ⅲ)配合物的Mossbauer谱及其他光谱探讨它们的键合和结构。     

PREPARATION AND CHARACTERIZATION OF COBALT(III) COMPLEXES WITH SARCOSINE AND SOME TETRADENTATE LIGANDS OF THE EDDA TYPE

Abstract

Meridional geometrical isomers of cobalt(III) complexes with sarcosine (N-methylglycine) and tetradentate ligands edda (ethylenediamine-N,N′-diacetate ion), eddp (ethylenediamine-N,N′-di-3-propionate ion) and 1,3-pdda (1,3-propylenediamine-N,N′-diacetate ion) have been prepared. The edda and eddp cobalt(III) complexes were made by the reaction of sarcosine and sodium ethylenediamine-N,N′-diacetato(carbonato)cobaltate(III), and sodium uns-cis-(ethylenediamine-N,N′-di-3-propionato)(carbonato)cobaltate(III) dihydrate, respectively. The previously synthesized pdda-cobalt(III) complex with sarcosine was obtained by a new route by direct synthesis of cobalt(II) chloride hexahydrate with sarcosine and 1,3-pdda in the presents of lead(IV) oxide. Complexes were isolated chromatographically and characterized by elemental analysis, electron absorption spectra, infrared spectra and ¹H NMR spectroscopy.     

以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)-Fe(Ⅲ)和Mn(Ⅱ)-Mn(Ⅱ)双核配合物的合成与磁性

基于铁和锰的双核配合物在生物氧化还原过程中的重要作用及在化学的氧化还原过程中可能做为催化剂的应用前景,本文合成了两个新的以氯醌酸二价阴离子为桥联配体的Fe(Ⅲ)双核和Mn(Ⅱ)双核配合物:[Fe_2(phen)_4(μ-CA)](ClO_4)_4·2H_2O(1)和[Mn_2(phen)_4(μ-CA)](ClO_4)_2·3H_2O(2)(phen=1,10菲咯啉;CA=氯醌酸二价阴离子)。经元素分析、IR、电子光谱及磁性等测定,对两配合物进行了表征。     

若干锰(Ⅲ)希夫碱配合物的合成和表征

合成了六种锰(Ⅲ)希夫碱配合物:Mn(bzacem)X(X~-=Cl~-,Br~-,I~-,NCS~-,NO_2~-)和Mn(bzacen)ClO_4·2H_2O,其中bzacen~(2-)为N,N′-二(苯甲酰丙酮缩)-乙二胺阴离子.用NMR法测定配合物在DMSO溶液中的有效磁矩值为4.46—4.63,表明为高自旋配合物,将电子光谱中的吸收带分别按配位场带、荷移带和配体带进行了归属,在配合物的红外光谱中,原配体H_2bzacen中的ν_(N-H)带消失,ν_(C-O)带移向低频,并对Mn-O、Mn-N和Mn-X的伸缩带进行了归属。     

STEREOCHEMISTRY OF SIX-COORDINATE OCTAHEDRAL SILICON(IV) COMPLEXES CONTAINING 2,2-BIPYRIDINE

Abstract

[Si(bpy)₃]⁴⁺ (bpy = 2,2′-bipyridine), synthesized from Sil₄ and 2′.-bipyndine. was optically resolved by a chromatographic method using an SP-Sephadex C-25 column as an adsorbent and a 0.16M aqueous solution of sodium (2R,3R)-(-)-O,O′-dibenzoyltartrate as an eluent. The optical isomers were characterized by measurement of their electronic absorption, circular dichroism, and ¹H NMR spectra. The chromatographic resolution of [SKbpyb]⁴⁺ was also attempted with an aqueous solution of potassium [(2R,3R)-(+)-tartrato]antimonate(III). sodium (2R,3R)-(+)-hydrogentartrate, and sodium (2R,3R)-(+)-tartrate as eluents. Force-field calculations were used to elucidate the chromatographic elution mechanism. [Si(OH)₂(bpy)₂]I₂was also synthesized from Sil₄ and 2′,-bipyridine. The optical resolution of this complex was achieved with sodium [(2R,3R)-(+)-tartrato]antimonate(III).     

SYNTHESIS AND CHARACTERIZATION OF THE FORMAL Ni(III) AND Cu(III) COORDINATION COMPLEXES OF THE NEW 1,2-DITHIOLENE, 1,4-BUTANEDIYLDITHIOETHYLENE-1,2-DITHIOLATE

Abstract

The new 1,2-dithiolene, 1,4-butanediyldithioethylene-1,2-dithiolate, has been isolated. In addition, new monoanionic bis-complexes with nickel and copper have been prepared and isolated. The formal Ni(III) complex crystallizes in the orthorombic space group, P_bca, with a = 9.762(9), b = 12.53(2), and c = 23.166(3) Å, with 4 molecules in the unit cell. The structure was refined to an R = 9.01% (R_w = 8.95%). The formal Cu(III) complex crystallizes in the monoclinic space group, C_2/c, with a = 25.567(6), b = 8.011(3), c = 14.504(3) Å, and β = 106.17(2)° with 4 molecules in the unit cell. The structure refined to R = 4.2% with R _w = 4.3%. Comparisons to similar 1,2-dithiolenes suggest this ligand produces only modest structural and electronic differences when compared to the 1,3-propanediyldithioethylene-1,2-dithiolate complexes. The oxidation (to a neutral complex) and reduction (to a dianion) for the Ni(III) and Cu(III) complexes show large differences from those of maleonitriledithiolate. Other physical data are presented as well.     

R、S-三[N-(邻-氧α-萘亚甲基)-α-苯乙胺]合钴的合成、晶体结构及分子绝对构型

合成了R,S一三[N-(邻-氧α-萘亚甲基)-α-苯乙胺]合钴。x射线单晶衍射衍射测定了晶体结构及分子的绝对构型。晶体属正交晶系,D_2~4-P2_12_12_1空间群,晶胞参数:α=12.587(3),b=14.166(3),c=25.652(14)(?),v=4574.2(?)~3,z=4。用重原子法及差值Fourier合成解出结构,最后的R值为0.074。利用Co~( )对CuKa反常散射测定了分子的绝对构型。Co~( )为六配位,d~2sp~3杂化近正八面体构型。     

SOLVATION OF ALUMINIUM(III) AND IRON(III) COMPLEXES OF HYDROXAMATE LIGANDS IN ALCOHOL-WATER MIXTURES

Abstract

Solubilities and derived transfer chemical potential trends are reported for several tris(hydroxamato)-aluminium(III) and iron(III) complexes in methanol-water and in t-butylalcohol-water solvent mixtures. These trends are discussed in terms of hydrophilic and hydrophobic characteristics of the peripheries of these complexes.     

SYNTHESIS AND CHARACTERISATION OF A NEW NIOBATE COMPLEX WITH CHROMIUM(III)

Abstract

A new hexaniobate complex with chromium(III) was prepared and characterised by analytical and spectroscopic techniques. The compound is a violet, non-crystalline solid, formulated as [Cr₂(μ-OH)(H₃Nb₆O₁₉)(en)₃(H₂O)]. It was synthesised in aqueous solution by reaction of [Cr(en)₃]³⁺, en = ethylenediammine, with the hexaniobate anion [Nb₆O₁₉]^8-, at pH 8. Thermal decomposition yielded a mixture of CrNbO₄ and Nb₂O₅. The synthesis of this compound shows that the hexaniobate anion may form complexes at lower pH values than previously reported.     

希土高氯酸盐与N,N''''—二(2—吡啶亚甲基)—1,2—乙二胺配合物的合成及性质研究

自六十年代以来,希土离子与芳香胺及其衍生物的配合物研究受到人们的普遍重视。文献工作表明,N,N’-二(2-吡啶亚甲基)-1,2-乙二胺(简写为bpme)可与希土离子形成1:1型的配合物,但希土离子与该配体的1:2型固体配合物文献中尚未报道。为了探讨bpme与希土离子形成非1:1型配合物的可能性,我们在甲醇介质中合成出希土高氯酸盐与bpme的1:2型固体配合物,并对其性质进行了研究。     

A PROTON NMR STUDY OF THE STEREOCHEMISTRY AND KINETICS OF THE REACTIONS OF DIMETHYL SULFOXIDE WITH POTASSIUM DICLOROGLYCINATOPLATINATE(II) AND ITS METHYL DERIVATIVES

Abstract

Amino acid complexes of general formula K[Pt(NO)Cl₂], where NO denotes the metal bonded atoms of the amino acid, react completely with solvent DMSO to yield two products, cis- and trans-Pt(NO) (DMSO)Cl, where cis and trans refer to positions of DMSO relative to coordinated nitrogen. The products were identified and kinetic data were obtained from changes in the proton nmr spectra of the amino acid, when DMSO-d₆ was the solvent, or of both amino acid and coordinated DMSO, when ordinary DMSO was the solvent. For glycine and π-aminoisobutyric acid complexes, the rate of displacement of trans chloride exceeds that of cis chloride by a factor of 3. However, subsequent equilibration favors the cis isomer over the trans isomer by a factor of 10. By contrast, for the corresponding N, N-dimethyl derivatives, the rates of formation of the two isomers are more nearly the same and the equilibrium ratio does not differ from the kinetic ratio. In addition to providing a sensitive technique for evaluating small differences in kinetic trans-effects, these observations strongly suggest that the stereochemistry of Pt(NO) (DMSO)Cl for the corresponding alanine complex described by Kukushkin and Guryamava should be denoted cis, rather than the trans reported.     

高效液相色谱法研究铂(Ⅱ)配合物的配体交换反应

本文用高效液相色谱法研究了[Pt(TMDACP)I_2]和[Pt(TMDACP)(Cl-Ac)_2](TMDA是1,2,2-三甲基-1,3-二氨基环戊烷,Cl-Ac是氯乙酸根)的配体交换反应,测得20±0.1℃二级速率常数和平衡常数分别为(8.67±0.37)×10~(-3)mol~(-1)dm~3s~(-1)和0.572±0.008。     

CRYSTAL STRUCTURE OF THE ISOMORPHOUS COMPLEXES TETRAAQUABIS(2,6-DIHYDROXY-BENZOATO-O)(2,6-DIHYDROXY-BENZOATO-O,O)TERBIUM(III) AND HOLMIUM(III) DIHYDRATE

Abstract

The structures of isomorphic Tb(III) and Ho(III) complexes with 2,6-dihydroxybenzoic acid of formula [Tb(C₇H₅O₄] 2H₂O and [Ho(C₇H₅O₄)₃ 4H₂O] 2H₂O has been determined by X-ray diffraction and refined to a residual R = 0.030 for 5376 observed reflections and R = 0.0284 for 5660 observed reflections, for Tb(III) and Ho(III) complexes, respectively. Crystals are triclinic, space group P1 with a= 10.748(2), b=11.309(2), c = 12.452(2)Å, α = 82.28(3), ? = 73.05(5), γ = 68.27(3)° for Tb(III) and a= 10.731(2), b=11.269(2), c = 12.436(2)Å, α = 82.25(3), β = 72.92(3), γ = 68.46(3)° for Ho(III).

In the structure of these monomelic complexes the metal ions are coordinated by oxygen atoms of one bidentate chelating and two monodentate carboxylate groups and four molecules of water. Tb-O distances are in the range 2.323(3)-2.506(3) Å and Ho-0 2.297(3)-2.486(3) Å. The crystal structure, consisting of discrete units of neutral complexes with two molecules of water of crystallization is stabilized by intra-and intermolecular hydrogen bonds.     

希土高氯酸盐与N,N''—二(2—吡啶亚甲基)—1,2—乙二胺配合物的合成及性质研究

自六十年代以来,希土离子与芳香胺及其衍生物的配合物研究受到人们的普遍重视。     

The Spectropolarimetric Back-Titration of Rhodium(III) with the Chiral Ligand (R,R)-(-)-Trans-1, 2-Cyclohexanediaminetetraacetic Acid

Abstract

Spectropolarimetric back-titrations are described for rhodium(III); the optically active ligand (R, R)-(-)-t?ans-l, 2-cyclohexanediaminetetraacetic acid (R, R(-)CDTA) is used as the complexing agent and cadmium(II) ion as the back-titrant. The optical rotation is monitored throughout the titration, and the optically active ligand and stereospecifically formed complexes serve as self-indicators. The end points are determined graphically by straight-line extrapolations from a plot of volume-corrected observed rotations versus ml of titrant. The rhodium(III) titration plots are representative of normal spectro-polarimetric back-titrations. The range of analyses of rhodium(III) was from 40–0.5 mg.     

STRUCTURE CHARACTERIZATION AND CATALYTICACTIVITY TEST OF Ni(II) COMPLEXES CONTAINING2-(DIPHENYLPHOSPHINOAMINO) PYRIDINE(PAP)

IntroductionIn1962,N.V.Kutepow'SgroupfirstusedcomplexesofFe,CoandNiascatalyststocatalyzecarboXylationofethanoltopreparepropanoicacidanditsderivants.Thereactionpressurewashighandtheyieldwaslow.LateronPaulalsandhiscolleagueusedabC13andiodineascatalyst,which…     

COPPER(III) DITHIOCARBAMATE COMPLEXES FROM THIURAM DISULFIDES AND COPPER(I) HALIDES

Abstract

Tetraalkylthiuram disulfides react with Cu(I) halides to give materials of composition Cu₂(dtc)₃X₂, which are presumed to be the ionic species Cu (dtc)₂ ⁺Cu (dtc)X₂ ⁺ containing Cu(II) and Cu(III), on the basis of magnetic susceptibilities, IR and ESCA spectroscopies. In the presence of triphenylphosphine, sulfur abstraction from the monosulfides leads to known monosulfide complexes of Cu(I). Some of the dithiocarbamate complexes are also accessible through degradation of alkylimonium trithiolane and tetrathiolane halocuprate(I) compounds.     

DIASTEREOSELECTIVE SYNTHESIS AND STEREOCHEMISTRY OF (Z)-1-[3-ARYL-2-(PHENYLSULFANYL)-2-OXIRANYL]-1-ETHANONES

Diastereoselective synthesis of a series of (Z)-1-[3-aryl-2-(phenylsulfanyl)-2-oxiranyl]-1-ethanones was effected from the reaction of (Z)-4-aryl-3-(phenylsulfanyl)-3-buten-2-ones with alkaline hydrogen peroxide in tetrahydrofuran. The stereochemistry of the oxiranes has been deduced from two-dimensional NOESY spectrum.     

SYNTHESIS AND CHARACTERISATION OF DIORGANOANTIMONY(III) COMPLEXES OF THIOSEMICARBAZONES

Abstract

The interaction of the sodium salts of thiosemicarbazones with diphenylantimony chloride in 1:1 molar ratio in benzene solution lead to the formation of derivatives, Ph₂Sb[SC(NH₂)NN: C(R)R′] where R = H; R′ [dbnd] C₆H₅, CH₃OC₆H₄, C₆H₅CH[dbnd]CH, and R′ [dbnd] CH₃; R′[dbnd]C₆H₅, CH₃OC₆H₄, C₆H₄CH₃, respectively. The resulting complexes have been characterised on the basis of elemental analyses and molecular weight determination. The mode of bonding of the ligands with the metal atom has been proposed on the basis of I.R., ¹H and ¹³C NMR studies. All these ligands are found to behave as monofunctional bidentate moiety in these complexes.