钯-柠檬黄-表面活性剂荧光光度法的研究与应用

本文研究了在各种类型的表面活性剂存在下, 钯与柠檬黄的胶束增敏荧光反应, 测定了金属荧光配合物的形成条件、组成、量子产率、表观稳定常数和激发波长处的摩尔吸光系数, 对胶束增敏作用机理进行了初步探讨. 确定了测定钯的最佳条件, 钯在0.1-8.0μg/25mL 范围内与荧光强度呈线性关系, 检出下限达8.0x10^-^4μg/mL. 本文方法可不经分离直接快速地测定贵金属矿样中痕量钯,结果令人满意。     

Synthesis of a bis(phenoxyketimine) palladium(II) complex and its activity in the Suzuki-Miyaura reaction

The synthesis of a new charge-neutral, air- and moisture-stable fluorinated bis(phenoxyketimine) Pd(II) complex is presented. Its activity as a precatalyst in the Suzuki-Miyaura cross-coupling reaction of activated and unactivated bromides has been explored.     

Synthesis of palladium nanoparticles by reaction of filamentous cyanobacterial biomass with a palladium(II) chloride complex

The interaction of cyanobacterial biomass (Plectonema boryanum UTEX 485) with aqueous palladium(II) chloride (PdCl2 degrees ) has been investigated at 25-100 degrees C for up to 28 days. We report that the release of organic materials from the cyanobacteria promoted the precipitation of Pd(0) as crystalline spherical and elongate nanoparticles (< or =30 nm), both in solution and as dispersed and encrusted nanoparticles on cyanobacterial cells. In contrast, under abiotic conditions at 100 degrees C, palladium hydride (PdHx) was the principal palladium phase precipitated, with only minor amounts of palladium metal.     

Synthesis of palladium(II) and nickel(II) complexes with tetrabenzoporphine

Palladium and nickel complexes with tetrabenzoporphine were synthesized by reacting tetrabenzoporphine and cadmium tetrabensoporphine with palladium and nickel chlorides in boiling dimethylformamide and identified.     

Synthesis of 2,3-disubstituted indole using palladium(II)-catalyzed cyclization with alkenylation reaction

The reaction of ethyl 2-ethynylphenylcarbamate derivative with alkenes in the presence of a palladium(II) catalyst, copper dichloride and tetrabutylammonium fluoride (TBAF) produced 2-substituted 3-ethenylindoles during refluxing. The intramolecular cyclization reaction of ethyl 2-ethynylphenylcarbamates, which have an ethenyl part in the ethynyl group, was also used to produce carbazole derivatives.     

Unusual course of the reaction of N-(tosylmethyl)thiourea and N-(azidomethyl)thiourea with sodium enolate of dimedone

The end product of the reaction of N-(tosylmethyl)thiourea or N-(azidomethyl)thiourea with sodium enolate of dimedone is bis(2-hydroxy-4,4-dimethyl-6-oxocyclohex-1-enyl)methane (methylenebisdimedone) instead of the expected 8a-hydroxy-7,7-dimethyl-2-thioxoperhydroquinazolin-5-one.M. V. Lomonosov State Academy of Fine Chemical Technology, Moscow 117571, Russia; Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 70–72, January, 2000.     

Synthesis and characterization of palladium(II) and platinum(II) complexes with ferrocenylimidazole

The synthesis and characterization of ferrocenylimidazole complexes of platinum(II) and palladium(II) are described. Reaction of ferrocenylimidazoles with K₂MCl₄ (M = Pd, Pt) using a biphasic system of dichloromethane and ethanol/water provided the corresponding complexes 2a–2j in good yields. New synthetic routes for the synthesis of ferrocenylbenzylethers 2k–2o, bis(4-ferrocenylbenzyl)carbonate [2p] and 4-ferrocenylbenzylacetate [2q] are also described. These products were obtained by the reaction of 4-ferrocenylbenzyl-1H-imidazole-carboxylate and K₂PtCl₄ under various conditions. Compounds 2k–2o were also obtained by alternative routes which do not involve the use of a platinum salt. The crystal structures of 2b, 2q and plausible mechanisms for the formation of 2k, 2p and 2q are reported.     

The palladium(II)-catalyzed Nazarov reaction

The PdCl(2)-catalyzed cyclization of alpha-alkoxy dienones leads to 2-hydroxycyclopentenones, whereas the Pd(OAc)(2)-catalyzed reaction leads to cross-conjugated cyclopentenones through an oxidative process. [reaction: see text]     

Cationic palladium(II), platinum(II) and ruthenium(II) complexes containing a chelating difluoro-substituted thiourea ligand

The fluorine substituted thiourea 2,6-F₂C₆H₃C(O)NHC(S)NEt₂ was prepared in good yield from the reaction of 2,6-F₂C₆H₃C(O)Cl with KSCN and Et₂NH in acetone. Using this compound several heteroleptic, monocationic Pd(II), Pt(II) and Ru(II) complexes of the type cis-[M{κ²S,O-2,6-F₂C₆H₃C(O)NC(S)NEt₂}(L)]PF₆ [M = Pt, Pd; L = (Ph₃P)₂, ^tBu₂bipy, 1,10-phen] as well as [Ru(η⁶-p-cym){κ²S,O-2,6-F₂C₆H₃C(O)NC(S)NEt₂}(PPh₃)]PF₆ were prepared in high yields. The compounds were characterised by spectroscopic methods and, in one case, by single crystal X-ray diffraction.     

Synthesis and characterization of some methyl complexes of palladium(II). Part 2(1)

Summary Dichloro complexes of Pd^II, [Pd(L–L)Cl₂], where L–L=1-(thiomethyl)-2-(diphenylarsino)ethane (S–As) or 1-(thiomethyl)-2-(diphenylphosphino)ethane (S–P) andtrans-[PdL₂Cl₂], where L=diphenyl(2-phenylethyl)-phosphine (PE), diphenyl(1-naphthyl)phosphine (PN) orN-methyl-2-thiophenealdimine (SN), have been prepared and characterized. The reactions of these complexes with MeLi were investigated. The dimethyl complexes [Pd(L–L)Me₂] (L–L=S–As, S–P) and [Pd(PE)Me₂] were isolated and characterized. Reaction of [Pd(L–L)Me₂] (L–L=S–As, S–P) with HCl affords the monomethyl derivatives [Pd(L–L)Me(Cl)]. In contrast to the Pt analogues, [Pd(L–L)Me₂] and [Pd(L–L)Me(Cl)] are relatively less stable than [Pt(L–L)Me₂] and [Pt(L–L)Me(Cl)].     

Spectroscopic,structure and DFT studies of copper(II) and palladium(II) complexes of pyridine-2-carboxaldehyde-2-pyridylhydrazone: A chromogenic agent for palladium(II)

A heterocyclic hydrazone ligand, pyridine-2-carboxaldehyde-2-pyridylhydrazone, HL, 1, was investigated as a new chromogenic agent for selective detection of Pd²⁺. The ligand HL, 1, undergoes 1:1 complexation with Pd²⁺ and Cu²⁺ to form complexes [Pd(L)Cl], 1a and [Cu(HL)Cl₂], 1b respectively. The complex 1a gives a characteristic absorption peak at 536 nm with distinct reddish-pink coloration. The change in color can easily be distinguished from other metal complexes by the naked eye. No obvious interference was observed in the presence of other metal ions (Na⁺, K⁺, Mg²⁺, Ca²⁺, Al³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Sn²⁺, Hg²⁺, Pb²⁺). The association constants, K_ass (UV–Vis), were found to be 5.52 ± 0.004 × 10⁴ for 1a and 4.94 ± 0.006 × 10⁴ for 1b at 298 K. On excitation at 295 nm, the ligand HL, 1 strongly emits at 372 nm due to an intraligand ¹(π–π^∗) transition. Upon complexation the emission peaks are blue shifted (λ_ex 295 nm, λ_em 358 nm for 1a and λ_ex 295 nm, λ_em 367 nm for 1b) along with a quenching (F/F₀ 0.32 for 1a and 0.88 for 1b) in the emission intensity. DFT and TDDFT calculations were highly consistent with the spectroscopic behavior of the ligand and complexes. The molecular structure of the complex 1b has been determined by single crystal X-ray diffraction studies.     

Synthesis and characterization of copper(II), nickel(II) and cobalt(II) complexes with novel thiourea derivatives

A novel series of thiourea derivatives, namely, N,N-diphenyl-N-(4-phenyl-benzoyl)thiourea (HL¹), N,N-diphenyl-N-(4-chloro-benzoyl)thiourea (HL²) and N,N-di-n-propyl-N-(4-chloro-benzoyl)thiourea (HL³), and its metal complexes has been prepared and characterised by elemental analysis, i.r. spectroscopy, ¹H-n.m.r. spectroscopy, mass spectrometry and single crystal X-ray diffraction. The ligand coordinates to Ni^II, Cu^II and Co^II in a bidentate manner yielding essentially neutral complexes of the type cis-[ML₂]. N.m.r. spectra and single crystal X-ray diffraction analysis revealed the presence of a distorted tetrahedral coordination ML₂ complex.     

4-(2-噻唑偶氮)-苯二甘氨酸的合成及其与钯显色反应的研究

报道了水溶性 4 ( 2 噻唑偶氮 ) 苯二甘氨酸 (TAPC)新试剂的合成。该试剂对钯具有较高灵敏度和选择性。在 0 .5mol/LHNO3介质中 ,TAPC与Pd(Ⅱ )形成 2∶1蓝色配合物 ,最大吸收波长 632nm。钯浓度在 0 μg/mL～ 1 .6μg/mL范围内符合比耳定律 ,表观摩尔吸光系数ε632 =5× 1 0 4 L·mol- 1 ·cm- 1 。可允许许多离子共存 ,可直接用于含钯分子筛样中微量钯的测定     

Experimental and quantum chemical studies of structure and vibrational spectra of platinum(II) and palladium(II) thiourea chlorides

Equilibrium geometries of platinum(II) and palladium(II) tetrathiourea dichlorides have been determined by the X-Ray diffraction studies as well as calculated by the Density Functional Theory using the MPW1PW/LanL2DZ functional/basis set. Infrared spectra of the species have also been studied in the 4000–400 cm⁻¹ frequency range both experimentally and theoretically. The experimental and theoretical data remain in satisfactory agreement.     

Synthesis and characterization of cyclometallated palladium(II) and platinum(II) complexes with amide-thiolate ligands

The redox reaction of bis(2-benzamidophenyl) disulfide (H₂L-LH₂) with [Pd(PPh₃)₄] in a 1:1 ratio gave mononuclear and dinuclear palladium(II) complexes with 2-benzamidobenzenethiolate (H₂L⁻), [Pd(H₂L-S)₂(PPh₃)₂] (1) and [Pd₂(H₂L-S)₂ (μ-H₂L-S)₂(PPh₃)₂] (2). A similar reaction with [Pt(PPh₃)₄] produced only the corresponding mononuclear platinum(II) complex, [Pt(H₂L-S)₂(PPh₃)₂] (3). Treatment of these complexes with KOH led to the formation of cyclometallated palladium(II) and platinum(II) complexes, [Pd(L-C,N,S)(PPh₃)]⁻ ([4]⁻) and [Pt(L-C,N,S) (PPh₃)]⁻ ([5]⁻). The molecular structures of 2, 3 and [4]⁻ were determined by X-ray crystallography.     

Spectrophotometric determination of glucosamine and its analogous amino sugars with o-hydroxyhydroquinonephthalein and palladium(II).

A simple and highly sensitive spectrophotometric method for the determination of glucosamine and its analogous amino sugars was established based on fading of the palladium(II)-o-hydroxyhydroquinonephthalein-hexadecyltrimethylammonium complex. In the determination of glucosamine, Beer's law is obeyed in the range of 0.02 - 0.18 microg ml(-1), with an effective molar absorptivity at 630 nm and the relative standard deviation being 8.4 x 10(5) dm3 mol(-1) cm(-1) and 1.08% (n = 10). This method is about 70-times more sensitive than the Elson-Morgan method. The method was successfully applied to the assay of glucosamine in actual samples.