Promoting of non-transition metal alkylation with organyl halides in the presence of binary systems based on an organometallic compound and a transition metal compound: I. Hypothetical stepwise scheme and verification of the system efficiency

A hypothetical scheme has been proposed for the alkylation of non-transition metals with organyl halides in the presence of binary systems consisting of an organometallic compound and a transition metal compound. The scheme implies catalysis by transition metal atoms, small clusters, and subhalides adsorbed on the surface of metal to be alkylated. These particles are formed during the process as a result of interaction between the binary system components. The alkylation of commercial zinc powder with ethyl bromide has been used as a model reaction to demonstrate that the binary system ethylzinc bromide-copper(I) iodide is superior in its efficiency and experimental simplicity to all other examined methods for stimulation of the alkylation of elements with organyl halides yielding organometallic compounds.     

Promoting nontransition metal alkylation with organic halides in the presence of binary systems based on an organometallic compound and a transition metal compound: V. Effect of the nature of the transition metal compound in the binary system on the rate of a steady-state process

The example of alkylation of commercial zinc and cadmium powders with organic halides in the presence of binary systems comprising an organometallic and a transition metal compounds was used to show that the nature of the transition metal compound in the binary system strongly affects the rate of a steady-state process. Therewith, the significant factors are both the nature of the transition metal and the ligand composition. It was found that the activity of the binary systems correlates with the activity of the transition metal compound in the transmetalation reaction with the organometallic component of the binary system (reduction of the transition metal compound).     

Promoting non-transition metal alkylation with organic halides in the presence of binary systems based on an organometallic compound and a transition metal compound: VIII. Selectivity of the binary systems action

Selectivity of action of binary systems based on an organometallic compound and a transition metal compound in a direct synthesis of organometallic compounds via alkylation of metals with organic halides has been considered. Study of the side reactions in the course of zinc and cadmium powders alkylation (gaseous hydrocarbons evolution) taken as an example has demonstrated that the increase in activity of the binary system components is accompanied by decrease in its selectivity. The intensity of the side reactions is steeply increased above certain temperature determined by the nature of the reactants and components of the binary system. The surface of the alkylated metal containing adatoms and small clusters of the transition metal promotes the side processes.     

Promoting non-transition metal alkylation with organic halides in the presence of binary systems based on an organometallic compound and a transition metal compound: VII. Additional details of the mechanism

Mechanism of metals alkylation with an organic halide in the presence of binary systems has been defined in more detail. It has been shown that the passivating film on the surface of zinc and cadmium is partially preserved in the course of the process, and the reaction in diethyl ether is decelerated due to the competitive adsorption of the organyl halide and diethyl ether on the surface of the reacting metal. The ratelimiting stages of the studied alkylation process have been elucidated basing on the experimental data on the effect of the reagents (organyl halide and alkylated metal) nature on the rate of the steady-state reaction and modeling of the suggested catalytic cycle.     

Transition metal compound surfaces

Studies of transition metal compound surfaces using modern surface science techniques are reviewed. Studies of the surface structure and composition of model transition metal compound surfaces are emphasized. The growth of the transition metal compound surface from a chemisorbed layer is used as an introduction to investigations of the surface properties of macroscopic single crystals of transition metal compounds. Examples of both binary and tenary compound systems are examined in relation to chemisorbed layer studies. Although only a few systems are chosen to illustrate work in this field, extensive references to other studies and other systems are included.     

Promoting non-transition metal alkylation with organic halides in the presence of binary systems based on an organometallic compound and a transition metal compound: VI. Effect of various additives on the rate of the steady-state process

The effect of various additives such as transition and non-transition metal oxides, hydroxides, and salts on the rate of steady-state alkylation of commercial zinc powder with ethyl bromide in the presence of ethylzinc bromide–copper(I) iodide binary system has been studied. Most of the examined compounds either do not affect the reaction rate or reduce it. Only addition of zinc(II) bromide, zinc(II) hydroxide, and water appreciably accelerates the process. Mechanism of action of the additives is discussed.     

Promoting alkylation of non-transition metals with organic halides in the presence of binary systems based on organometallic compound and transition metal compound: II. Comparative study of efficiency of various agents in the course of destruction of passivating film on the surface of alkylated metal

It has been demonstrated that alkylzinc halides efficiently destroy the passivating film on the zinc-copper pair in the course of its alkylation with ethyl bromide to give ethylzinc bromide. The alkylzinc halides efficiency is comparable to that of ethyl iodide and exceeds that of salts of transition or non-transition metals as well as of ultraviolet irradiation. Addition of alkylzinc halides or metal salts as well as ultraviolet irradiation have practically no effect on the developed reaction. The results have demonstrated that the organometallic component of the binary systems is polyfunctional; this permits a generalization of known features of a number of known methods promoting direct synthesis of organometallic compounds.     

Binary mixtures of metal compounds as flame retardants for organic polymers

Studies have been made of the effect on the flammability of thermoplastic polymers of the partial or total replacement of one metal compound by another in the presence also of a suitable halogen compound; particular attention has been paid to systems where the primary flame retardant is antimony(III) oxide. With each binary metal compound system investigated, ten different compositions have been chosen so as to provide a symmetrical arrangement of points within a triangular design; resulting calculated values of the limiting oxygen index for each polymer-flame retardant system for a given polymer are shown as a graphical contour analysis. Comprehensive studies of several systems show that both iron(III) oxide and aluminium oxide monohydrate can significantly enhance the flame-retardant action of antimony(III) oxide but that several other metal compounds, although not as effective as Sb₂O₃, may nevertheless be used as adequate partial replacements for it. The Fe₂O₃-SnO₂-H₂O system can also act as an effective flame retardant under certain conditions. The SnOZnO system perhaps best illustrates the importance of the polymer substrate and of the total additive loading as factors controlling the flame-retardant effectiveness. For all the systems studied, however, ABS is a much better substrate than HDPE. The results of a reasonably detailed study of the flame retardance conferred by several different compositions of a binary metal compound mixture give a much more reliable indication of the effects on polymer flammability of the constituent metal compounds than are obtained simply by replacement of a given concentration of one compound by another.     

Amide-water interactions in cosolvent systems. I. Solubilities and apparent molar volumes of methyl paraben

Solubility and apparent molar volume data are used to demonstrate effects of amide alkylation on amide-water interactions at 25° C. Precise measurements were made of the apparent molar volumes of the amides in binary amide-water mixtures using a dilatometric technique. The results show that the apparent molar volumes of alkyl-substituted amides in water pass through a minimum at an amide concentration which varies inversely with the degree of alkylation. Further studies showed that the solubilities of methyl paraben (methyl-p-hydroxybenzoate) and naphthalene in various amide-water solvent systems increased in characteristic fashion with amide alkylation.     

Melting diagrams of quaternary systems with a single compound

Topological analysis was made of the structure of the melting diagrams of quaternary systems with a single compound. Graphs of phase diagrams were constructed, which show the relative positions of invariant points and monovariant lines on the liquidus hypersurface. It was shown that there exist two types of diagrams with a binary compound and six types of diagrams with a ternary compound. Quaternary compound C can form by congruent crystallization reaction L = C (I) or by the interaction of melt with components: L + K₁ = C (II), L + K₁ + K₂ = C (III), or L + K₁ + K₂ + K₃ = C (IV). There are 23 types of diagrams with reaction (I) and 23 types of diagrams with reaction (II), which described by identical graphs; 25 types of diagrams with reaction (III); and 6 types of diagrams with reaction (IV). Fragments of the obtained diagrams correspond to various topological situations, which may occur in more-component systems.     

Determination of rhenium in the URe2 binary compound by differential spectrophotometry

A differential spectrophotometric determination of rhenium in its binary compound with uranium is described; the method is based on the action of tin(II) chloride on perrhenate in the presence of dimethylglyoxime with measurement at 445 nm. Uranium does not interfere. For solutions containing about 1 mg of rhenium, the coefficient of variation was 0.08%.     

Use of binary metal deposits on a cylindrical carbon-fiber microelectrode in the voltammetric determination of metal ions

The effect of binary metal deposits on a cylindrical carbon-fiber microelectrode on the determination of metals by direct and stripping voltammetry was studied. The electrolytic deposition of a binary system of copper and thallium, cadmium, lead, or mercury on the electrode in an alkaline solution resulted in the disappearance of the electroreduction peak of dissolved oxygen in the potential range from -0.8 to -1.4 V and in a decrease in the background current. Under the conditions of limited diffusion, the peak currents of Ni(II), Co(II), and Zn(II) in differential pulse voltammograms were 3–7 times higher than those calculated for a reversible electrode process under the conditions of semi-infinite diffusion. Because of this, the determination limit for metal ions in direct voltammetry was lowered to 1 X 10^-6 M. With a binary copper-thallium system, the peak current of zinc(II) reduction can be be detected in the presence of 5000-fold molar amounts of copper(II). The deposition of binary copper-lead and copper-thallium systems under the conditions of limited diffusion reduced the effect of negative interaction between the components of these systems and made possible the determination of lead(II) and thallium(I) by stripping voltammetry using additional peaks.     

Structural and electronic properties of compound metal clusters

The equilibrium geometries, relative stabilities, and vertical ionization potentials of compound clusters involving Li _n , Na, Mg, and Al atoms have been calculated using ab initio self-consistent field linear combination of atomic orbitals — molecular orbital (SCF-LCAO-MO) method. The exchange energies are calculated exactly using the unrestricted Hartree-Fock (UHF) method whereas the correlation correction is included within the framework of configuration interaction involving pair excitations of valence electrons. While the later correction has no significant effect on the equilibrium geometries of clusters, it is essential for the understanding of relative stabilities. Clusters with even numbers of electrons are found to be more stable than those with odd numbers of electrons regardless of their charge state and atomic composition. The equilibrium geometries of homo-nuclear clusters can be significantly altered by replacing one of its constituent atoms with a hetero-nuclear atom. The role of electronic structure on the geometries and stabilities of compound clusters is discussed.     

Application of calorimetry and DTA to metal systems

The calorimetric methods employed for the study of metal systems (solution, combustion, direct reaction calorimetry) are considered and briefly discussed with respect to each other.The development of apparatus for the calorimetry of metals and alloys is examined as a whole, with particular reference to the progressive increase of the maximum limit of the working temperature.The employment of calorimetric methods for the determination of equilibrium phase diagrams is described according to two different approaches: (1) corresponding to classical DTA, based on the identification of phase boundaries by the exploration of the system as a function of temperature, at constant composition; (2) corresponding to the measurement of partial and integral enthalpies of alloy formation as a function of the composition, at constant temperature.A brief report is given of the utilization of calorimetric data for the computation of equilibrium phase diagrams and equations are also given that allow the equilibrium temperature to be calculated between a liquid solution (binary or multicomponent) and a pure component (or an intermetallic compound) as a function of the thermodynamic parameters obtained by calorimetric methods.     

Voltammetric stripping analysis of metal concentrates with polymers soluble in aqueous solutions

The conditions were worked out for the simultaneous stripping voltammetric determination of components of the ternary Pb(II)-Cu(II)-Cd(II) and binary Ag(I)-Cu(II) systems at a carbon-paste electrode in 2% aqueous solutions of the water soluble polymer polyethyleneimine (PEI) and its thiourea-containing derivative (TU-PEI). Water-soluble polymers are shown to reduce the mutual effects of the components of the binary and ternary system at the electrode surface. The different complex stability of Ag(I), Pb(II) or Cd(II) and Cu(II) with PEI and TU-PEI allows Ag(I), Pb(II) and Cd(II) to be determined in the presence of a large excess of Cu(II).     

Extraction and validation of substructure profiles for enriching compound libraries

Compounds known to be potent against a specific protein target may potentially contain a signature profile of common substructures that is highly correlated to their potency. These substructure profiles may be useful in enriching compound libraries or for prioritizing compounds against a specific protein target. With this objective in mind, a set of compounds with known potency against six selected kinases (2 each from 3 kinase families) was used to generate binary molecular fingerprints. Each fingerprint key represents a substructure that is found within a compound and the frequency with which the fingerprint occurs was then tabulated. Thereafter, a frequent pattern mining technique was applied with the aim of uncovering substructures that are not only well represented among known potent inhibitors but are also unrepresented among known inactive compounds and vice versa. Substructure profiles that are representative of potent inhibitors against each of the 3 kinase families were thus extracted. Based on our validation results, these substructure profiles demonstrated significant enrichment for highly potent compounds against their respective kinase targets. The advantages of using our approach over conventional methods in analyzing such datasets and its application in the mining of substructures for enriching compound libraries are presented.     

Voltammetric stripping analysis of metal concentrates with polymers soluble in aqueous solutions

The conditions were worked out for the simultaneous stripping voltammetric determination of components of the ternary Pb(II)-Cu(II)-Cd(II) and binary Ag(I)-Cu(II) systems at a carbon-paste electrode in 2% aqueous solutions of the water soluble polymer polyethyleneimine (PEI) and its thiourea-containing derivative (TU-PEI). Water-soluble polymers are shown to reduce the mutual effects of the components of the binary and ternary system at the electrode surface. The different complex stability of Ag(I), Pb(II) or Cd(II) and Cu(II) with PEI and TU-PEI allows Ag(I), Pb(II) and Cd(II) to be determined in the presence of a large excess of Cu(II). Received: 17 July 1997 / Revised: 1 December 1997 / Accepted: 3 December 1997     

Reissert compound studies. LXVII. The pyrido[3,4-b]pyrazine reissert compound

The pyrido[3,4-b]pyrazine systems investigated were found to form Reissert compounds in the presence of an acyl halide (or chloroformate) and trimethylsilyl cyanide. Only the mono Reissert compounds were isolated. In the case of 2,3-diphenylpyrido[3,4-b]pyrazine ( 7 ), its reaction with benzene sulfonyl chloride and trimethylsilyl cyanide gave 5-cyano-2,3-diphenylpyrido[3,4-b]pyrazine ( 16 ). Alkylation of the Reissert compound 11 and analog 12 either directly gave the alkylated hetercyclic base or the alkylated Reissert analog compound.     

Sodium-potassium synergism in the alkylation of toluene and naphthalene with ethene in C10H8−Na−K systems in THF

Sodium-potassium synergism in the alkylation of toluene and naphthalene with ethene in naphthalene-alkali metal systems in THF was discovered. In the case of toluene, the maximum synergistic effect is observed at an Na∶K molar ratio of 1∶1. With this Na∶K molar ratio, the yields of the products of toluene alkylation with ethene considerably increase. The efficiency of naphthalene alkylation (in the presence of toluene) is also markedly enhanced on replacement of sodium or potassium by their mixture.     

Vibrational dynamics, intermolecular interactions, and compound formation in GeH4-H2 under pressure

Optical microscopy, spectroscopic and x-ray diffraction studies at high-pressure are used to investigate intermolecular interactions in binary mixtures of germane (GeH(4)) + hydrogen (H(2)). The measurements reveal the formation of a new molecular compound, with the approximate stoichiometry GeH(4)(H(2))(2), when the constituents are compressed above 7.5 GPa. Raman and infrared spectroscopic measurements show multiple H(2) vibrons substantially softened from bulk solid hydrogen. With increasing pressure, the frequencies of several Raman and infrared H(2) vibrons decrease, indicating anomalous attractive interaction for closed-shell, nonpolar molecules. Synchrotron powder x-ray diffraction measurements show that the compound has a structure based on face-centered cubic (fcc) with GeH(4) molecules occupying fcc sites and H(2) molecules likely distributed between O(h) and T(d) sites. Above ca. 17 GPa, GeH(4) molecules in the compound become unstable with respect to decomposition products (Ge + H(2)), however, the compound can be preserved metastably to ca. 27 GPa for time-scales of the order of several hours.