Search results for "Reaction"

A Copper‐Catalyzed Synthesis of Pyrroles through Photochemically Generated Acylazirines

2019

Electrochemical studies on organometallic compounds—xx. Electrogeneration of an unusual organometallic derivative of ruthenium(I)

1989

Abstract The two-electron reduction of dinuclear ruthenium complexes [RuCl 2 (η 6 - p -cymene)] 2 ( p -cymene = p -CH 3 C 6 H 4 CH(CH 3 ) 2 ] give the corresponding relatively stable ruthenium(I) dimer derivative. The same species can also be obtained by electrochemical reduction of the cationic complexes [(η 6 - p -cymene)Ru(μ-Cl) 3 Ru(η 6 - p -cymene)]PF 6 . A redox mechanism is proposed.

Mechanistic Studies on the Metal-Free Activation of Dihydrogen by Antiaromatic Pentarylboroles

2012

The perfluoro- and perprotiopentaphenylboroles 1 and 2 react with dihydrogen to effect H-H bond cleavage and formation of boracyclopentene products. The mechanism of this reaction has been studied experimentally through evaluation of the kinetic properties of the slower reaction between 2 and H(2). The reaction is first-order in both [borole] and [H(2)] with activation parameters of ΔH(‡) = 34(8) kJ/mol and ΔS(‡) = -146(25) J mol(-1) K(-1). A minimal kinetic isotope effect of 1.10(5) was observed, suggesting an asynchronous geometry for H-H cleavage in the rate-limiting transition state. To explain the stereochemistry of the observed products, a ring-opening/ring-closing mechanism is propos…

Methylation of 2-phenylamino-1,3,4-thiadiazole. A structure debated

1987

The true identity of the 4-methyl-5-phenylimino-δ2-1,3,4-thiadiazoline (A) has been demonstrated. The reactions, previously reported in the literature to give A have been repeated and the structure of the compounds obtained has been established.

Study of the thermal behaviour of ordered bimetallic EDTA complexes

1986

Abstract The study of the thermal behaviour of a family of isostructural ordered bimetallic MM'(EDTA)·6H 2 O complexes has been performed using TG and DTA. Formal kinetic analysis of the dehydration step has been approached using non-isothermal procedures. The resulting correlation among the calculated E a values and the cationic sizes implies a common dehydration mechanism. Copper-containing complexes show distinctive behaviour during the ligand pyrolysis processes. A mechanistic interpretation involving formation of Cu(I) and Cu(0) intermediates is furnished. The evolution of the inorganic residues in systems containing both Co and Ni is especially considered given the interest in the (Co…

Kinetic study of methoxide-promoted elimination reactions of some 1,1,1-trichloro-2,2-bis(phenyl-substituted)ethanes

2001

The methoxide-promoted elimination reaction of some 1,1,1-trichloro-2,2-bis(phenyl-substituted)ethanes (1) was investigated. The ortho-substituted derivatives were found to be less reactive than the corresponding ortho-unsubstituted derivatives, irrespective of the nature of their substituent. The reactivity data were correlated with the 13C NMR chemical shift values of C-β of either 1,1,1-trichloro-2,2-bis(phenyl-substituted)ethanes or 1,1-dichloro-2,2-bis(phenyl-substituted)ethenes and the better result was obtained for the former correlation. Activation parameters for the methoxide-promoted elimination of 1 show very similar values for ortho-substituted derivatives. The total data set se…

Direct electrochemical detosylation of tetratosylcyclen to cyclen with carbon cathodes

2005

The electrochemical detosylation of tetratosylcyclen to cyclen (1,4,7,10-tetraazacyclododecane) in aprotic solvents at a carbon cathode was investigated both in a bench-scale batch electrochemical reactor and in a continuous batch recirculation reaction system equipped with a parallel-plate electrochemical cell. Yields and faradaic efficiency in cyclen, respectively, of 80 and 55% were obtained in the bench-scale reactor working in acetonitrile. It was found that the faradaic efficiency in cyclen depends on the competition between the reduction of the tetratosylcyclen and parasitic processes as the reduction of the tetraalkylammonium cations present in the supporting electrolyte. We have ob…

Study of the thermal decomposition of bromazepan complexes with Co(II), Ni(II), Cu(II) and Zn(II)

1984

Abstract The thermal behaviour of complexes of bromazepan with Co(II), Ni(II), Cu(II) and Zn(II) was studied by thermogravimetry (TG) and differential thermal analysis (DTA). The complexes decompose in two steps: dehydration and decomposition. A correlation between the dehydration temperatures of MB2Xn and the coordinating ability of X is observed.

Pd-catalyzed hydrodehalogenation of chlorinated olefins: Theoretical insights to the reaction mechanism

2012

Abstract Density functional theory calculations are applied to study energetics of trichloroethene (TCE) hydrodechlorination over pure Pd(1 1 1), chlorine-covered Pd(1 1 1), and Pd island supported by Au(1 1 1). Our results show that in all cases C Cl bond breakings take place more readily than C H bond formations and that TCE dechlorinates fully producing CCH precursors for the hydrogenations. The reaction pathway through radical-like species provides a possible explanation to the experimental product distributions that show a nominal amount of lesser chlorinated species in the presence of excess hydrogen. The surface chlorine resulted from the TCE decomposition weakens the binding of the …

1990

The anionic polymerization of tert-butyl acylate (tBuA) initiated by tert-butyl α-lithioisobutyrate was investigated in THF at 25°C. The individual oligomers were isolated and characterized by UV, IR and NMR spectroscopy. The distribution of products was determined in the range of reaction times 0,02 s ≤ t ≤ 1800 s. The oligomerization is extremely fast. Even after 0,02 s at -30°C, no residual monomer could be detected. After short reaction times the reaction mixture almost exclusively consists of linear oligomers of tBuA. This indicates that there is no termination reaction by Claisen condensation during polymerization. Nevertheless, the molecular weight distribution is rather broad (Mw/Mn…