Hydrazine derivatives in the synthesis of linear and heterocyclic compounds

N-Siloxycarbonylation, transamination, carboxylation, silylation, and condensation of N,N-dimethylhydrazine, 1-methyl-1-[2-(1-methylhydrazino)ethyl]hydrazine, N-methyl-2-(1-methylhydrazino)ethanamine, and some their trimethylsilyl derivatives resulted in the formation of previously unknown linear and heterocyclic compounds.     

Investigation of the structure and energetics of Β-diketonates. VIII. Molecular structure of the Ba(dpm)2 monomer according to gas phase electron diffraction data

A combined electron diffraction and mass spectrometric study of the overheated vapor over barium dipivaloylmethanate was performed. It was found that at 488°C the monomeric molecular form predominates in the vapor. The Ba(dpm)₂ molecule has D_2d symmetry. Its r_a, r_g, and r_α parameters were determined.     

S-ArylN,N-dialkylamidothiosulfates, a novel class of sulfenic acid derivatives

A method for the synthesis ofS-arylN,N-dialkylamidothiosulfates, a novel class of sulfenic acid derivatives, was proposed. The method is based on the reaction of arenesulfenyl chlorides withN,N-dialkylamidosulfinic acids or with secondary amines in liquid SO₂ in the presence of triethylamine. In the presence of halogen-containing Lewis acids,S-arylN,N-dialkyl-amidothiosulfates add to the C=C bonds to give aryl β-haloalkyl sulfides. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1484–1487, August, 2000.     

Complexes of Lanthanide (Dy,Er, Yb) Thiocyanates with Tetramethylphenanthroline. Synthesis,Thermolysis, and SMM Properties

Russian Journal of Coordination Chemistry - The mononuclear neutral complexes [Ln(Me4Phen)2(H2O)(NCS)3]·Me4Phen·0.75EtOH (Ln = Dy, Er, Yb) were prepared for the first time by the reaction...     

Analysis of composition profiles to obtain interdiffusion coefficients in binary intermetallic compounds

Intermetallic compounds containing high concentrations of structural vacancies have made the determination of the interdiffusivity from the composition profile from a diffusion couple a confusing issue. In this paper, an exact procedure is formulated from fundamental principles. The only assumption made is the use of the Gibbs–Duhem relation. We show that the standard procedure for analysing composition profiles in diffusion couples slightly overestimates the interdiffusivity. We also show that the procedure put forward by Kim and Chang (Metall. Mater. Trans., 31A () 1519) to analyse the composition profiles in NiAl is incorrect near the stoichiometric composition where it seriously underestimates the interdiffusivity.     

The molecular structure of tris-2,2,6,6-tetramethyl-heptane-3,5-dione aluminium: gas-phase electron diffraction,quantum chemical calculations and X-ray crystallography

Structural Chemistry - The molecular structure of tris-2,2,6,6-tetramethyl-heptane-3,5-dione aluminium, or Al(thd)3, has been determined by quantum chemical (DFT) calculations, X-ray...     

Prediction of kinetic demixing in a quaternary mixed oxide (A,B, C)O in an oxygen potential gradient

Kinetic demixing in quaternary mixed oxides has not been investigated previously, either theoretically or experimentally. In this theoretical study, we derive simple and exact analytical expressions that describe the steady-state cation concentration profiles resulting from kinetic demixing in mixed oxides of the (A, B, C)O type. The concentration profiles are expressed in terms of cation-vacancy exchange frequency ratios. We assume a random distribution of cations and make use of the Moleko-Allnatt exact sum-rule expression relating the phenomenological coefficients in the ternary random alloy to the vacancy mechanism operative. We employ Monte Carlo simulation of kinetic demixing to verify the result of the analysis. We discuss how kinetic demixing profiles can be processed to obtain atom-vacancy exchange frequency ratios. We also discuss how atom-vacancy exchange frequencies themselves might be obtained from available diffusivities in the quaternary oxide.     

Analysis of vacancies produced at non-equilibrium concentrations by interdiffusion

In this paper, we address the fundamental problem of chemical interdiffusion in binary alloys for the case where vacancies at non-equilibrium concentrations may be generated during the interdiffusion process. We take a very general phenomenological approach to interdiffusion but develop it in a new way. Both high vacancy and low vacancy concentrations are dealt with. For the commonly encountered small vacancy concentration case our strategy centres on directing the information about the driving force associated with the non-equilibrium vacancies (which is effectively not measurable) onto the velocity of inert marker(s) in the diffusion zone. Assuming access to independent knowledge of the two tracer diffusivities we derive expressions for the transport coefficient (for the case of non-equilibrium vacancies) using an analysis along Boltzmann–Matano lines. Using the random alloy model we show that in principle it is possible to measure the relative concentration of non-equilibrium vacancies produced during interdiffusion.     

Atom transport in random two sublattice structures: analogue of the random alloy sum rule

A simple and often used model of atom transport by the vacancy mechanism on two physically distinct interpenetrating sublattices assumes that each atom–vacancy exchange frequency depends only on the species of the atom and the sublattice from which it jumps. In the kinetic theory of this model, the phenomenological coefficients can be expressed as sums of partial correlation functions, each labelled by the sublattices associated with the atoms making the first and last jumps in the sequence of correlated jumps which it represents. A sum rule, a set of exact relations among these partial correlation functions, is derived for the model, assuming arbitrary vacancy content and any number of chemical species. It reduces to a widely used sum rule for the random lattice gas [L.K. Moleko and A.R. Allnatt, Phil. Mag. A 58 677 (1988)] in the limit that atom jump frequencies are made independent of sublattice. For the two sublattice model at very low vacancy contents, a more powerful sum rule is also derived; it is essentially the same as that of Belova and Murch [Defect Diffus. Forum 194/199 547 (2001)]. The efficiencies of the three sum rules are briefly compared. The low vacancy concentration sum rule is illustrated by numerical simulations for a binary two sublattice system.     

Release of a diamond-like film on a nickel surface irradiated simultaneously with carbon ions and electrons

Nickel samples at temperatures of 300–1000°C have been irradiated simultaneously with 10-to 30-keV C⁺ ions and 1-to 5-keV electrons. The release of implanted carbon atoms on the surface of a sample with the formation of a transparent carbon film with the prevailing sp ³ hybridization has been observed. The thickness of the film is several tens of nanometers. The formation of films is attributed to the acceleration of the formation of carbon structures in samples irradiated by accelerated electrons.