Reaction of early transition metal complexes with macrocycles. II. Synthesis and structure of TiCl3(H2O) · 18-crown-6, a compound with a unique bidentate bonding mode for the 18-crown-6 molecule

18-crown-6 reacts with TiCl₃ in CH₂Cl₂ to form a complex in which the crown ether functions as a tridentate ligand. Addition of moist hexane affords a molecular complex in which the crown ether functions as a bidentate ligand. A water molecule is bonded directly to the titanium atom and is further hydrogen bonded to three of the oxygen atoms of the crown. The deep blue crystals of the CH₂Cl₂ adduct belong to the monoclinic space groupP2₁/n witha=13.481(8),b=8.021(5),c=21.425(9) Å, =97.32(5)°, and _calc = 1.51 g cm^–3 forZ=4. Refinement led to a conventionalR value of 0.040 based on 873 observed reflections. The Ti–O bond distances for the crown oxygen atoms are 2.123(8) and 2.154(9) Å, while the oxygen atom of the water molecule is bonded at 2.072(8) Å. The octahedral coordination sphere of the titanium atom is completed by the three chlorine atoms at distances of 2.340(5), 2.352(4), and 2.373(4) Å. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82034 (10 pages).     

The influence of the salt concentration on the aggregation behavior of viscoelastic detergents

The influence of excess NaCl on the properties of viscoelastic detergent solutions of Cetypyridiniumsalicylate (CPySal) has been studied by static and dynamic light scattering, electric birefringence and rheological measurements. It is obeserved that the rodlike micelles of length L which are present in these solutions and which are responsible for their elastic properties grow in length with the increase of the NaCl concentration. As long as the rods are shorter than their mean distance, their length can be determined from the rheological and electric birefringence measurements. For very small shear fields these solutions behave as Newtonian fluids. The viscosity of the solution increases strongly when the rods begin to overlap. Solutions with overlapping rods are elastic. It is postulated from the results that the cmc_II (the critical concentration above which rods are present) and the length L of the rods are partially determined by the intermicellar interaction energy. It is furthermore postulated that this intermicellar interaction energy has an influence on the polydispersity of the rods and seems to make the rods relatively monodisperse.     

Functionalized organosilica microspheres via a novel emulsion-based route

Thiol-functionalized organosilica microspheres were synthesized via a two-step process: (1) acid-catalyzed hydrolysis and condensation of 3-mercaptopropyltrimethoxysilane (MPTMS), followed by (2) base-catalyzed condensation, which led to the rapid formation of emulsion droplets with a narrow size distribution. These droplets continued to condense to form solid microspheres. Solution (29)Si NMR and optical microscopy were applied to study the mechanism of this novel synthetic route. Solid-state (29)Si NMR, SEM, zeta potential titration, and Coulter counter measurements were used to study the bulk and surface properties and to determine the particle size distributions of the final microspheres. Compared to conventional St?ber silica particles, these microspheres were shown to have a lower degree of cross-linking (average degree of condensation, r = 1.25), a larger average size (up to 6 microm), and a higher isoelectric point (pH = 4.4). Confocal microscopy of dye-labeled microspheres showed an even distribution of dye molecules throughout the interior, characteristic of a readily accessible and permeable organosilica network. These findings have implications for the production of functionalized solid supports for use in catalysis and biological applications, such as optically encoded carriers for combinatorial synthesis.     

Chemical analysis of rain and snow samples from Chernogolovk/Russia by IC, TXRF and ICP–MS

 Data are reported for a first measurement campaign for a great number of cations (the range of concentrations for main components is given in ng/mL: Na:<70–880; Mg: 12–160; Al:<7–120; K: 200–1600; NH₄ ⁺: 2500–9000; Ca: 300–2500; Fe:<140–1200; Zn: 20–320) and anions (HCOO^-: 100–1800; CH₃COO^-: 400–14500; C₂O^2- ₄: <100–460; NO^- ₂: <20–55; NO^- ₃: 660–9900; SO^2- ₃:<100–1150; SO₄ ^2-: 450–19700; Cl^-: 170–3200) in rain and snow samples of the Chernogolovka region 80 km northeast of the centre of Moscow. These data serve as a first assessment of the situation of the atmosphere in this region. For the determination of fluoride, formate, acetate, nitrite, bromide, nitrate, sulfite, and sulfate by IC, a relevant development of the method was carried out. For some metallic cations, a critical quality control was achieved by parallel measurements with ICP-MS, TXRF, and IC. Furthermore, time resolved measurements were performed for a rain event. Filtration experiments were undertaken to differentiate between the presence of a series of elements and species in liquid or solid state in the collected aqueous samples. Received: 25 July 1996 / Revised: 26 September 1996 / Accepted: 13 October 1996     

The protection of uracil and guanine residues in oligonucleotide synthesis

The protection of uracil and 2-$\text{N}$-acyl guanine residues with 4-$\text{O}$-phenyl [or 4-$\text{O}$-(2,4-dimethylphenyl)] and 6-$\text{O}$-(2-nitrophenyl) groups as in $\text{7a}$ [or $\text{7b}$] and $\text{9}$, respectively, is described. These $\text{O}$-aryl protecting groups, which appear to withstand the usual conditions of oligonucleotide synthesis, may readily be removed by treatment with 2-nitrobenzaldoximate ions.     

Hybrid catalysts: the synthesis, structure and ethene polymerisation activity of (salicylaldiminato)(pyrrolylaldiminato) titanium complexes

The mono(salicylaldiminato) complexes Ti{3-tBu-2-(O)C6H3CH=N(R)}Cl3(THF)(where R = C6H5, C6F5) react with the metallated pyrrolylaldiminato ligand, K[2-(C6H5NCH)C4H3N], to afford the first examples of hybrid salicylaldiminato-ligated octahedral titanium complexes; the pre-catalysts give from very high to extremely high ethene polymerisation productivities when activated with MAO.     

The interaction between TEOS and some polyols

Hybrid organic-inorganic materials, silica – polyols (ethylene-glycol – EG; 1,2 propane diol – 1,2PG; 1,3 propane diol – 1,3PG and glycerol – GL), were prepared by a sol-gel process starting from tetraethylorthosilicate (TEOS) and polyols, in acid catalysis. The resulting materials were studied by thermal analysis (in air and nitrogen), FTIR and solid state ²⁹Si-NMR spectroscopy. These techniques evidenced the presence of polyols in the silica matrix both hydrogen bounded and chemically bounded in the silica network. The thermal analysis proves to be the most appropriate technique to evidence the organic chains linked in the matrix network and to follow the thermal evolution of the gels to the SiO₂ matrix.     

Procedures for the enhancement of selectivity in liquid phase chemiluminescence detection

An overview of liquid phase chemiluminescence (CL) processes is presented and the potential for CL detection in liquid chromatography (LC) is discussed, with particular reference to the luminol and peroxyoxalate reactions. Post column ion displacement from a solid phase reagent [a cation exchange resin in the copper(II) form] followed by catalysis of the luminol reaction is used for the quantification of mixtures of weak acids after separation by ion-exclusion chromatography. Polyaromatic hydrocarbons (PAHs) released during the combustion of biomass fuels are separated by reversed-phase chromatography and quantified by their sensitizing effect on the peroxyoxalate reaction. This procedure is also used for the determination of carboxylic acids in non-aqueous media after selective pre-column derivatization with a fluorescent label (9-anthracenemethanol).     

Ruthenium-catalysed conversion of 1,4-alkynediols into pyrroles

Various 1,2,5-substituted pyrroles have been synthesised from 1,4-alkynediols using a ruthenium catalysed isomerisation to give the corresponding 1,4-dicarbonyl compounds, which undergo in situ cyclisation to pyrroles in the presence of amine.     

An electron spin resonance study of radicals from chloramine-t-1 : Spin trapping of radicals produced in acid media

Under acid conditions aqueous solutions of chloramine-T form nitrogen-centred radicals via loss of the chlorine atom. The nitrogen radicals produced have been studied by ESR spectroscopy using the spintrapping method. Adducts of the spin trap phenyl-t-butyl nitrone are oxidized by chloramine-T in acid media to give a paramagnetic product in which the unpaired electron interacts with two inequivalent nitrogen atoms. The spin trap 5,5-dimethyl-2-pyrrolidine-1 -oxide is oxidized rapidly to 5,5-dimethyl-2-pyrrolidone-1-oxyl by chloramine-T under acid onditions. The water soluble trap α-4-pyridyl-1-oxide-N-t-butyl nitrone forms a stable nitroxide adduct with a nitrogen radical of chloramine-T in acid solution. Identical results were obtained with chloramine-B (sodium salt of N-chlorobenzene sulfonamide), indicating the involvement of the N-chloramine group in radical formation.