三核钨钼簇合物对苯乙烯氧化反应的催化

关于烯烃的催化氧化,报道较多。Takao等研究了苯乙烯在Ir和Rh络合物存在下的氧化反应;Collman曾报道环己烯在Vaska络合物[IrX(CO)(PPh_3)_2]催化下氧化成环己酮和环已烯氧化物。本文采用Cotton合成的簇合物[W_3O_2(CH_3CO_2)_6(H_2O)_3]Br_2·     

钨的溶剂萃取

本文简要地讨论了钨的溶剂萃取,重点讨论了萃取剂的结构对钨的萃取性能以及金属分离的影响。     

Acid-catalyzed attack of the dinitrogen ligand in thecis-(Me2PhP)4Mo(N2)2 andtrans-(Ph2PCH2CH2PPh2W(N2)2 complexes by nitronium and nitrosonium cations with the formation of nitrogen oxides

The interaction of labeled dinitrogen complexescis-(Me₂PhP)₄Mo(¹⁵N₂)₂ andtrans-(dppe)₂W(¹⁵N₂)₂ with non-labeled nitronium and nitrosonium fluoroborates,¹⁴NO₂BF₄ and¹⁴NOBF₄, in sulfolane at room temperature in the presence of H₂SO₄ results in rapid formation of labeled nitrous and nitric oxides (¹⁵N¹⁴NO,¹⁵NO), as well as¹⁵N¹⁴N. The yield of the products depends on the reagent ratio and reaches 10–20 mol. % per mole of a complex under optimum conditions. The mechanism of the reactions found is proposed. It involves the step of protonation of the dinitrogen ligand to form the corresponding hydrazido(2–) derivatives, which are then attacked by nitronium or nitrosonium cations. In accordance with the mechanism proposed, it was established that the hydrazido(2–) complexes, (Me₂PhP)₃Mo(¹⁵N₂H₂)Cl₂ and (dppe)₂W(¹⁵N₂H₂)Cl₂, are capable of forming¹⁵N¹⁴NO,¹⁵NO, and¹⁵N¹⁴N under the action of¹⁴NO₂BF₄ and¹⁴NOBF₄ in the absence of an acid.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 13–13, July, 1995.     

Novel Reactions of Organomolybdenum and Organotungsten Compounds: Additive–Reductive Carbonyl Dimerization,Spontaneous Transformation of Methyl Ligands into μ-Methylene Ligands,and Selective Carbonylmethylenation

Hitherto there was no reaction known that permits transformations of R¹R²-CO → 0.5 R¹R²R³C–CR¹R²R³ in one step. This type of additive–reductive carbonyl dimerization is now possible using alkoxy(alkyl)tungsten(v) complexes with aromatic, heteroaromatic or α,β-unsaturated aldehydes and ketones. When a corresponding phenyl complex was employed in a test experiment, it was revealed that an aliphatic ketone could be used as the substrate in this reaction. A second interesting type of reaction is the transformation of CH₃ ligands into μ-CH₂ ligands, which occurs during the treatment of MeLi or Me₃Al with molybdenum or tungsten chlorides (oxidation states VI and V, for Mo additionally IV) at low temperatures with liberation of CH₄. Here, the question arises as to whether the intermediate involved has a terminal CH₂ ligand (Schrock carbene complex) or a μ-CH₃ ligand (CH₃ bound by a two-electron three-center bond to two metal atoms). Of all the μ-CH₂ complexes obtained, those which were synthesized by the action of MeLi on molybdenum chlorides can be recommended as reagents for carbonylmethylenation of aldehydes and ketones. They display high selectivity, very low basicity, a surprising resistance to protons, they are readily available, can be easily modified and, as regards their selective behavior, they have been investigated more thoroughly than other readily accessible carbonylmethylenation reagents of comparable selectivity. The results of NMR spectroscopic investigations on the structure of the μ-CH₂ complexes, and associated reaction mechanisms are discussed. A survey of carbonylmethylenation reagents, which have been reported in the literature, permits comparisons to be made with carbonylmethylenating molybdenum and tungsten complexes.     

Hydrodeoxygenation of glycerol into propanols over a Ni/WO3–TiO2 catalyst

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Metathesis of hex-1-ene in ionic liquids catalyzed by WCl6

Metathesis of hex-1-ene in ionic liquids catalyzed by WCl₆ was studied. The metathesis is preceded by isomerization of hex-1-ene to hex-2-ene, from which the main reaction product, viz., oct-4-ene, is derived. The WCl₆-1-butyl-3-methylimidazolium tetrafluoroborate (BMIM·BF₄) system efficiently catalyzes metathesis of linear olefin, the ionic liquid serving as the reaction medium by forming a stable homogeneous catalytic system with WCl₆. The yields of the metathesis products increase with increasing reaction temperature. The addition of tin-containing promoters leads to a substantial increase in the reaction rate. In the WCl₆-BMIM·BF₄-SnBu₄ system, the selectivity of the formation of oct-4-ene is significantly enhanced.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2094–2097, October, 2004.     

Valorization of Zea mays hairs waste extracts for antioxidant and anticorrosive activity of mild steel in 1 M HCl environment

The extraction of Zea mays hairs (Z. mays) was carried out by soxhlet and ultrasound techniques and through three solvents. Phytochemical tests and quantitative analysis of total phenols content (TPC) and flavonoids content (FC) for all extracts were also determined. The antioxidant activity, for different fractions, was determined by using three methods; DPPH, FRAP and TAC. All extracts were rich in polyphenols and the analysis of TPC and FC showed that the hydro-ethanolic extract obtained by ultrasound was characterized by a significant amount of TPC and FC. The n-butanolic fraction was rich in FC and also had a very high antioxidant capacity. On the other hand, the inhibiting effect of hydro-ethanolic extract, n-butanolic fraction and standard (flavone) on mild steel corrosion in 1 M HCl solution was investigated by electrochemical measurements. The polarization curves along with EIS diagrams indicated that flavone was the major molecule responsible for inhibition and acted as mixed-type inhibitor with predominant control of cathodic reaction. The antioxidant activity of BF was well correlated to corrosion inhibition efficiency.     

An all solid-state electrochromic smart window

An all solid-state electrochromic smart window employing prussian blue and electrodeposited WO₃ film with poly (vinyl chloride) (PVC) gel electrolyte that has high conductivity (2 mS/cm) at room temperature has been fabricated for the first time. The smart window has beell found to be excellent for electrochromism and memory characteristics.     

二元矩阵值分叉连分式插值的矩阵算法

本文给出了一个计算二元矩阵分叉连分式插值的系数算法以及与此算法等价的矩阵算法,这种算法是用矩阵广义逆意义下定义的矩阵行、列初等变换而给出的．