Studies of the compositions of Pd(II) hydrolysis products

The characterization of the clusters formed on alkaline hydrolysis of [PdCl₄]^2– was performed using¹⁷O,²³Na,³⁵Cl,¹³³Cs NMR and UV spectroscopy. The chemical composition of the clusters was found to be [Pd(OH)₂] _n ·nNaCl. No mononuclear oxo- or hydroxocomplexes were detected. The spatial structure of the clusters is stabilized by alkali metal cations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 675–679, April, 1993.     

Catalytic Hydrosilylation of Furan, Thiophene, and Pyridine Aldimines

The addition of hydrosilanes (HSiEt₃, HSiMe₂Ph, H₂SiPh₂) to the CH=N bond of heterocyclic azomethines has been studied in the presence of monovalent complexes of rhodium and palladium. The effect on the reaction of the CF₃ group of the aldimines, which were obtained from O-, S-, and N-heteroaromatic aldehydes and 2-trifluoromethylaniline, has been clarified, as were other regularities of the processes being studied. A series of corresponding furans, thiophenes, and pyridine amines has been synthesized.     

Synthesis of vinyl-substituted oxiranes and their transformation to dihydrofurans

The reaction of dimethylsulfonium methylide with the carbonyl function of 2-arylidene-cyclohexanones obtained from 2-methylcyclohexanone affords the corresponding spirooxiranes. The application of this reaction to 2,2-dimethyl-6-(5-methylfurfurylidene)cyclohexanone and 2,2-dimethyl-6-(5-chlorofurfurylidene)cyclohexanone leads to substituted 4,4-dimethyl-1-furyl-1,-3,4,5,6,7-hexahydroisobenzofurans.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1439–1443, August, 1994.     

Nitrated polynuclear aromatic hydrocarbons in ambient air in Italy. A brief overview

When nitrated polynuclear aromatic hydrocarbons (NPAH) were recognised as long‐term toxic compounds and were also identified in several anthropogenic emissions and among the by‐products of photochemical smog they became objects of investigation in ambient air in both polluted and clean environments. In Italy the first investigations focussing on atmospheric NPAH were performed in the early eighties and encompassed both the canyon streets and dwelling areas of Rome. Because NPAH were indicated as markers of vehicle emission, new investigations were performed in other cities and also in rural and (nominally) unpolluted locations. In general, the first measurements of NPAH were episodic and could not be assumed to be strictly representative of the sites investigated. In contrast, nowadays consistent data bases on NPAH have been built up and are discussed in the technical literature, so that both neat concentrations and the yearly timed variation of the most important NPAH congeners have been measured in Italian air. Although concentrations of NPAH in air are usually much lower than those of PAH, owing to their very high potency in inducing mutations and tumours NPAH are regarded as having an important health impact on populations living in Italian urban areas. In this regard the genotoxicity of atmospheric aerosols is partly associated with nitrofluoranthenes and nitropyrenes whereas nitronaphthalenes and methylnitronaphthalenes seem to contribute to that of the gaseous organic fraction. Several civic and regional administrations are introducing control of atmospheric NPAH among ways of improving air quality in cities.     

杂氮硅三环成环反应的研究

本文报导了与硅原子直接相连的有机基团(R)对杂氮硅三环成环速率的影响。利用气相色谱检测成环反应的产物之一——乙醇的生成速率和数量,并同与硅相连的R基团对成环反应速率的影响作比较。实验结果表明五种杂氮硅三环成环速度顺序为Cl_2CH—>ClCH_2—>ClCH_2CH_2CH_2—>CH_2=CH—>CH_3—,这与理论推断相符。     

1-(α-萘乙酰基)-4-芳酰基氨基硫脲及3-(α-萘亚甲基)-4-芳酰基-1,2,4-三唑琳-5-硫酮的合成

许多酰氨基硫脲类衍生物有抗病毒、抗细菌、抗肿瘤等功效,我们曾经通过5-(α-萘)-2H-四唑-2-乙酰肼与芳酰异硫氰酸酯缩合得一系列新的酰氨基硫脲和相关的杂环衍生物,观察到它们在很低的浓度下就有调节小麦芽鞘生长的功能。Kothari等用α-萘乙酰肼与芳基异硫氰酸酯缩和制得一系列1-(α-萘乙酰基)-4-芳基氨基硫脲及     

An investigation of the aromaticity of transition metal heterocyclic complexes by conventional criteria and indices of aromaticity

Conventional criteria and indices of aromaticity, including electronic, geometric, energetic and magnetic aspects have been applied to examine the aromaticity of five typical transition metal heterocyclic complexes, i.e. six-membered osmabezene 1 and iridabenzene 2, five-membered cobaltacyclopentadiene 3 and iridacyclopentadiene 4, and four-membered tungstacyclobutadiene 5. The results show that the cyclic, planar, conjugated and Hückel 4n+2 rule’s criteria in the transition-metal-containing heterocycles of the five complexes studied are all met. Five quantitative aromaticity indices, including Bird aromatic index (I_n), homodesmotic reaction aromatic stabilization energy (HASE), absolute hardness (η), diamagnetic susceptibility exaltation (Λ) and NMR chemical shift (δH), qualitatively lead to a consistent and affirmative conclusion that all of them are aromatic. However, they fail to draw a common conclusion for their relative magnitudes of aromaticity, which proves once again the multidimensional character of aromaticity.     

Solid state reactions of nitrogenous heterocyclic compounds(Ⅰ)——Solid state reactions of 3-methyl-l-phenyl-5-pyrazolone with carbonyl compounds

The solid state reaction of 3-methyl-1-phenyl-5-pyrazolone (MPP) with aromatic aldehydes and ke-tones benzil derivatives and imides,and the solid state Michael addition reaction of MPP with 4-arylidene-3-methyl-1-phenyl-5-pyrnzolone 2 were investigated.Some new solid state reactions between the reactants were found,from which a series of new compounds were obtained The structures of the products were identified by IR,1H NMR,MS,elemental analyses and also by X-ray crystal analysis,and the reaction mechanism of MPP with aromatic aldehydes and ketones was proposed     

Structure of polynuclear palladium(ii) hydroxocomplexes formed upon alkaline hydrolysis of palladium(ii) chloride complexes

The structure of polynuclear Pd^II hydroxocomplexes (PHC) formed as a result of alkaline hydrolysis of Pd^II chloride complexes was studied by EXAFS, SAXS, and TEM methods. It is established that in aqueous solutions a hydroxocomplex particle is a filament curled into a ball containing about 100 Pd atoms. The filament consists of planar coordination squares of PdO₄ units linkedvia one or two oxygen bridges of different geometry. Aging of samples results in an increase in the number of single bridging ligands and a decrease in the diameter of particles. Interatomic distances around palladium atoms were determined.Translated fromIzvestiya Akademii Nauk. Seriya Khimlcheskaya, No. 10, pp. 1901–1905, October, 1995.     

2,8,9-三氧杂-5-氮杂-1-硼杂双环[3,3,3]十一碳烷的合成

本文报导了具有N→B配位键的2,8,9-三氧杂-5-氮杂-1-硼杂双环[3,3,3]十一碳烷的合成及性质。化合物(1)的制备已有报导,而化合物(2),(3)则为新的化合物。我们研究了它们的成环条件,制备的最佳条件及化学稳定性。