Cyanide attack at low-spin iron(II)–diimine complexes: the structure of a cyanide-containing derivative of a leaving ligand

The isolation and structural characterisation of the product of addition of HCN to the Schiff base derived from phenyl 2-pyridyl ketone and 3,4-dimethylaniline (Me2bsb) provides evidence in favour of a mechanism involving nucleophilic attack at the coordinated ligand for reaction of the complex [Fe(Me₂bsb)₃]²⁺ with cyanide.     

Rank-1 approximation to the van der Waals interaction

We present and discuss a variational single-product approximation to the van der Waals dispersion interaction leading to a simple formula for C ₆ that seems capable to give more than 99% of the ‘exact’ value. The formula is derived from Hylleraas’ variational principle in the tensor product space of the interacting molecules and therefore enjoys bounding properties. The formula has been tested by computing the C ₆ dispersion constants of H–H, and, at Full CI level, of the following systems: He–He, He–Li, Li–Li, LiH–LiH, HF–HF. Connections with the London formula are discussed. Contribution to the Fernando Bernardi Memorial Issue.     

Synthesis,characterization, X-ray structural analysis and study of oxidative properties of propyltriphenylphosphonium bromochromate

The complex of propyltriphenylphosphonium bromochromate(VI), PrPh₃P[CrO₃Br] is easily synthesized in nearly quantitative yield using a direct reaction of chromium(VI) oxide and propyltriphenylphosphonium bromide. This compound is a versatile reagent for the efficient and selective oxidation of organic substrates, in particular for alcohols to their corresponding aldehydes or ketones, under mild conditions. This compound was characterized by IR, UV/Visible, ¹³C-n.m.r. and ¹H-n.m.r. techniques. It crystallized in the monoclinic form and its crystal and molecular structure have been determined by X-ray crystallography.     

Microwave synthesis,characterization and catalytic properties of titanium-incorporated ZSM-5 zeolite

Titanium-incorporated ZSM-5 zeolites (Si/Al = 50–200 and Si/Ti = 70) were successfully synthesized in a one-step sol-gel process under microwave irradiation. The characteristics of Ti-ZSM-5 zeolites were investigated using X-ray power diffraction, UV/Vis-DRS, FT-IR spectroscopy and solid-state ²⁷Al-NMR to monitor the physico-chemical properties. Simultaneously, the acidic properties were characterized by the NH₃-TPD profile. The characterization results revealed that the Ti⁴⁺ and Al³⁺ ions were well incorporated into the framework of Ti-ZSM-5 zeolite. The prepared zeolite was moderately active but selective in the dehydration of methanol to dimethyl ether.     

Preparation and swelling properties of hydrolysis-resistant superabsorbent composite based on acrylic acid and sodium bentonite

Abstract

A novel hydrolysis-resistant superabsorbent composite was prepared via the solution polymerization based on acrylic acid (AA) and sodium bentonite (SBT) as monomers, tetraallylammonium bromine (TAAB) as crosslinker and ammonium persulfate (APS) as initiator. The mechanism of polymerization and the structure of the superabsorbent polymer (SAP) were studied by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (X-ray), and scanning electron microscopy (SEM). The reaction conditions such as different mass ratios of APS to AA, TAAB to AA, SBT to AA, neutralization degree of AA were optimized by orthogonal experiment, and the influence of each reaction condition on the capacity of water absorption at 150?°C was investigated via single-factor controlled experiment. The hydrolysis resistance and swelling kinetics of the SAP were studied in different solutions at 150?°C. Compared to traditional SAPs, the SAP synthesized with TAAB as crosslinker performed a more excellent hydrolysis resistance and water absorbency capacity at high temperatures. The water absorbency in distilled water or 0.1?mol L^?1 NaCl solution could reach 392.6 and 145.2?g g^?1at 150?°C, respectively. The SAP maintaining high swelling capacity in the pH range of 5–9 indicated its wide application values in the acidic or alkaline environment at high temperature. In addition, the SAP exhibited good reusability which could still retain about 73% of its initial water absorbency after reswelling six times at 150?°C.     

Cu-Zn-Sn体系富Sn区液相限的研究

近些年来,无铅低熔点填料日渐引起人们的兴趣,且将得到广泛的应用。Cu-Zn-Sn合金正是无铅低熔点填料的一种基本合金。该体系相图虽有一些报道,但他们的研究只涉及富铜区(>50Wt％)的液相限和等温截面(500℃)。我们颇感兴趣的富Sn区的液相限,尚未见文献报道,因此测定该体系富Sn区的液相限是必要的。关于Cu-Zn-Sn体系的三个相关二元体系,已有文献报道,也较成熟。对于Cu-Zn体系,富Zn区600℃以下存在两个转熔反应,其转熔点分别为Q(～88Wt％Zn,598℃),W(97.5-98.5Wt％Zn,424℃);Cu-Sn体系富Sn区有一个转熔反应,其转熔点     

Template synthesis in the nickel(II)–thiocarbohydrazide–propanone triple system

The complexing process proceeding in the Ni^II–thiocarbohydrazide (H₂N–H–NC(=S)–NH–NH₂)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of Ni^II with (N,N,S,S)-donor tetradentate ligands having NiL¹, NiL² and NiL³compositions where L¹ is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L² is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L³ is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur.     

缓慢炭化部分氧化对制备煤质活性炭的影响

研究了炭化升温速度、炭化低温区引入空气部分氧化对活性炭制备过程中炭化阶段、炭化物结构、活性炭性能等的影响。结果表明，炭化时低温部分氧化可提高炭化物得率，使炭化物微晶的ｄ００２值升高和Ｌｃ值减小；而较慢的炭化升温速度有利于制备优质活性炭。缓慢炭化、部分氧化可以在一定程度上控制炭化路径，使炭化向生成取向性差、难石墨化、各向同性、呒定形炭多的炭化物的方向进行；并讨论了它们控制炭化的作用机理。以此为指导，     

新型2-氧代-1,2,4-三唑并[3,2-d][1,5]苯并氧氮杂类稠杂环的合成

将取代色满酮(1)与芳肼反应生成的腙与HNCO发生[3+2]环加成反应,加成产物(2)经氧化得到偕偶氮异氰酸酯(3).化合物3在HBF4的催化下发生环化-重排反应,得到新颖的三环系2-氧代-1,2,4-三唑并[3,2-d][1,5]苯并氧氮杂化合物5a～5g.     

Effect of ionic additives on the elution of sodium aryl sulfonates in supercritical fluid chromatography

Addition of a small amount of polar solvent (i.e., modifier) to CO2 in packed column supercritical fluid chromatography (SFC) has shown major improvements in both polar analyte solubility and interaction of the polar analyte with the stationary phase. Recently, the addition of an ionic component (i.e., additive) to the primary modifier by one of us has been shown to extend even further the application of SFC to polar analytes. In this work, the effect of various ionic additives on the elution of ionic compounds, such as sodium 4-dodecylbenzene sulfonate and sodium 4-octylbenene sulfonate, has been studied. The additives were lithium acetate, ammonium acetate, tetramethylammonium acetate, tetrabutylammonium acetate, and ammonium chloride dissolved in methanol. Three stationary phases with different degrees of deactivation were considered: conventional cyanopropyl, deltabond cyanopropyl, and bare silica. The effect of additive concentration and additive functionality on analyte retention was investigated. Sodium 4-dodecylbenzene sulfonate was successfully eluted using all the additives with good peak shape under isocratic/isobaric/isothermal conditions. Different additives, however, yielded different retention times and in some cases different peak shapes.