Copper(I) complexes from copper(II) halides and 1,3-thiazohdine-2-thione

Summary Reaction of 1,3-thiazolidine-2-thione and copper(II) chloride and bromide in MeOH yields CuL₃X complexes. These react with an excess of copper(II) halide to give CuL₂X complexes. From their i.r. spectra, all the complexes seem to be S-bonded to the metal. Thev(CuCl) vibration is identified at 236 cm^–1.     

X-ray photoelectron spectra of Pd(II) and Pt(II) complexes with 1,3-thiazolidine-2-thione. A quantum mechanics study on the free ligand

Metal complexes of general formula M(ttz)2X2 (with M= Pd(II) or Pt(II); X = Cl or Br; ttz = 1,3-thiazolidine-2-thione) have been synthetized as crystalline compounds and studied by means of X-ray Photoelectron Spectroscopy (XPS). The chemical shift of core level signals showed that ttz is bonded to the metal through the thioketonic sulphur atom and that electronic charge redistribution in the ligand takes place after complexation. No metal-nitrogen bonds are present. This is consistent with the results of all the quantum mechanical models according to which hydrogen is bound to nitrogen, even in the hydrogen bonded complex, making the latter rather unavailable to coordination     

Binuclear copper(II) complex with 2-imidazolylbenzothiazole and bridged chloride ligands

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Mixed ligand palladium(II) and platinum(II) complexes of tertiary diphosphines and benz-1,3-imidazoline-2-thione,benz-1,3-oxazoline-2-thione or benz-1,3-thiazoline-2-thione

Palladium(II) and platinum(II) complexes containing the mixed ligands tertiary diphosphines Ph₂P(CH₂) _n PPh₂, (n = 1–4) and benz-1,3-imidazoline-2-thione, benz-1,3-oxazoline-2-thione or benz-1,3-thiazoline-2-thione have been prepared and characterized by elemental analysis, magnetic susceptibility, molar conductance and i.r. spectral data. ³¹P–{¹H}-n.m.r. data have been applied to characterize the produced linkage isomers.     

A copper(II) chloride complex of hexamethylenetetramine

Summary The 3CuCl₂·4hmta·2HCl·2H₂O complex (hmta=hexamethylenetetramine) has been obtained from acid solution. Spectroscopic and magnetic investigations indicate that, in the crystal structure of this compound, the polymeric chains, 3CuCl₂·2hmta·2H₂O, and hmta·HCl groups occur.     

A new chiral recognition in aminolysis of 3-acyl-4(r)-methoxycarbonyl-1,3-thiazolidine-2-thione with racemic amines

A chiral recognition was observed in aminolysis of 3-acyl-4(R)-methoxycarbonyl-1,3-thiazolidine-2-thione $\text{1}$ by racemic amine $\text{2}$ to give an optically active amide (S-excess) and amine (R-excess).     

An infrared spectroscopic investigation on N-methyl-1,3-thiazolidine-2-thione and -2-selone

An infrared investigation cm N-methyl-1,3-thiazolidine-2-thione and -2-selone in the range 4000-200 cm^?1 is reported. The v CS and v CSe vibrations give contributions to the absorptions around 1000 cm^?1 and below 600 cm^?1. The assignments are supported by comparison of their ir spectra with those of S- and Se-methiodides. The π-bond orders of the thio- and seleno-ketonic links in these compounds are higher than those found for 1,3-imidazolidine-2-thione and -2-selone.     

Reactions of 2-pyridylphenylacetonitrile with copper(II) chloride,copper(II) bromide,cobalt(II) chloride and cobalt(II) bromide

Reaction of 2-pyridylphenylacetonitrile with copper(II) chloride and copper(II) bromide in dry ethanol gives the hitherto unreported compound 1,2-di(cyano,phenyl,2′-pyridyl)ethane. The cobalt halides react with 2-pyridylphenylacetonitrile to form 1:1 complexes containing O-ethyl-2-phenyl-2-(2′-pyridyl)acetimidate as ligand. Removal of the ligand by the action of dry liquid ammonia on the complexes provides a better route to the pure imidate than the well known Pinner method.     

Investigation of a mercury(II) carbene complex: bis(1,3-dimethylimidazol-2-ylidene) mercury chloride

The reaction of 1,3-dimethylimidazolium chloride with Hg(O₂CCH₃)₂ afforded a bis(carbene)mercury(II) complex (2), which is characterized by multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁵N, and ¹⁹⁹Hg) and by single-crystal X-ray analysis. As a consequence of chloride-ion interaction with the mercury center, the C₂-Hg-C₂ angle in 2 is reduced to 161.4 (3)° compared to its near-linear value in complex 4 that contains perchlorate counterions. The C₂ resonance in the mercury complex 2 moves upfield by 36.96 ppm relative to the parent carbene (2), with a large ¹J_HgC = 2741.18 Hz. © 1996 John Wiley & Sons, Inc.     

3-苄氧羰基四氢噻唑-2-硫酮的晶体结构与量子化学研究

苄氧羰酰氯与四氢噻唑-2-硫酮在三乙胺存在下反应生成了3-苄氧羰基四氢噻唑-2-硫酮。在甲醇中培养了标题化合物单晶,用X射线衍射法进行了结构表征。晶体结构属三斜晶系,P1间群,晶体学参数:a=0.6274(2)nm,b=0.7340(3)nm,c=1.2976(4)nm;α=100.73(3)°,β=94.53(3)°,γ=103.28(3)°,Z=2,M_μ=4.30cm^-1.分子中的>C=O与>C=S基团处于C(4)-N-C(1)键的同侧,为顺式。用PM₃分子轨道方法研究了该化合物的电子结构,得到电荷和键序分布以及前线轨道等性质。     

Study of 3-methyl-5-hydroxy-5-(d-arabino-tetrahydroxybutyl)-thiazolidine-2-thione as a reagent for the spectrophotometric determination of copper

The nature of the coppercomplex formed with3-methyl-5hy-droxy-5-(d-arabino-tetrahydroxybutyl)-thiazolidine-2-thione(MHATT) has been investigated. The complex is formed at pH 4.5-7.0, has an absorption maximum at 432 mmu, and an extinction coefficient of 13.5 x 10(3). The reaction is highly selective and the reagent has negligible absorption at 432 mmu. Simple and direct spectrophotometric methods are described for the estimation of copper in steels, aluminium alloys, lead, zinc and water, with the reagent.     

The stereoselective addition of titanium(IV) enolates of 1,3-oxazolidin-2-one and 1,3-thiazolidine-2-thione to cyclic N-acyliminium ion. The total synthesis of (+)-isoretronecanol

(+)-Isoretronecanol (1) has been prepared in four steps and 36% overall yield via the diastereoselective addition of the titanium(IV) enolate derived from N-4-chlorobutyryl-1,3-thiazolidine-2-thione (3) to N-Boc-2-methoxypyrrolidine (5), which afforded 2-substituted pyrrolidine 7 in 84% yield (8:1 diastereoisomeric ratio), followed by reductive recovery of the chiral auxiliary and cyclization.     

Bis(N-propyl-1,3-imidazolidine-2-thione)gold(I) chloride: Crystal and molecular structure

Summary The crystal and molecular structures of bis(N-propyl-1,3-imidazolidine-2-thione)gold(I) chloride, [(PrImt)₂Au]Cl, has been determined from three-dimensional x-ray intensity data collected on a CAD4 diffractometer. The compound crystallizes in the monoclinic space group P2₁/n witha=7.195(7),b=15.283(3),c=15.899(6) Å, =91.7(1) and Z = 4. Atomic parameters were refined by full-matrix least-squares methods to the R value of 6.2% for 2272 observed reflections. Gold(I) exhibits the usual linear coordination with S(1)-Au-S(10) angle of 177.7(1)°. The two [Prlmt] molecules are arranged intrans configuration which is attributed to the effects of intermolecular H-bonding between N-H and the halogen. The Au-S bond length is compared with the corresponding bond length in several known structures in order to evaluate thetrans influence of phosphorus, sulfur and chloride ligands on the Au-S bond.     

Stereoselective addition of the titanium enolate of N-acetyl (4S)-isopropyl-1,3-thiazolidine-2-thione to five-membered N-acyl iminium ions

[reaction: see text] Addition of the chlorotitanium enolate of N-acetyl 4-isopropyl-1,3-thiazolidine-2-thione to five-membered, N-substituted N-acyl iminium ions furnished the corresponding Mannich-type addition products with good diastereoselectivity and in good yields. The synthetic utility of the addition product 8 was demonstrated in a chemospecific anti-aldol reaction with cinnamaldehyde. By using this strategy, we constructed three contiguous chiral centers with high stereocontrol employing the same chiral auxiliary. X-Ray crystallographic analysis of addition product 2 and aldol product 14 revealed their absolute stereochemistry.     

双氯芬酸铜(Ⅱ)、氯灭酸铜(Ⅱ)配合物合成及其清除O-2的作用

天然超氧化物歧化酶(SOD)可以专一地清除生物体内的超氧阴离子自由基O-2,从而可预防活性氧中毒、抗衰老、减少癌症等疾病的发生。但是SOD分子量大、不易透过细胞膜、在生物体内半衰期短并有异体抗原性、价格昂贵,临床使用受到很大限制。2 (2′,5′ 二氯 苯氨基) 苯乙酸(双氯芬酸)、2 (3′ 氯 苯氨基) 苯甲酸(氯灭酸)是二苯胺类衍生物,临床用作消炎镇痛药,有清除O-2的能力[1],而且活性稳定。本文制备的它们的Cu(Ⅱ)配合物,可作为SOD模拟物[2],且活性较高。1　实验部分1 1　主要试剂和仪器双氯芬酸钠(纯度99 5%河南汤阴永奈化工有限…