Reversible Insertion of Methyl Isothiocyanate into Copper(I)Aryloxides

MeNCS undergoes insertion into the copper(I)-aryloxide bond to form [N-methylimino(aryloxy)methanethiolato]-copper(I) complexes. This insertion occurs in the absence of ancillary ligands unlike the analogous insertion of PhNCS. The reaction with 4-methylphenoxide results in the formation of hexakis[[N-methylimino(4-methylphenoxy) methanethiolato]copper(I)] (1), which has been characterized by X-ray crystallography. Crystal data for 1: hexagonal , a = 12.365(3) Angstrom, c = 36.734(16) Angstrom, gamma = 120 degrees, Z = 3, V = 4863(3) Angstrom(3), R = 0.0306. Reactions of 2,6-dimethyl- and 4-chlorophenoxides also result in analogous copper(I) complexes 2 and 3. Addition of stochiometric amounts of PPh(3) to the oligomeric complexes typically results in the extrusion of MeNCS. The ease of extrusion is dependent on the substituents on the aryloxide, and this deinsertion is accelerated by water. However, the extrusion reaction is slow enough in the case of the N-methylimino(2,6-dimethylphenoxy)-methanethiolate complex and the isolation of an intermediate monomeric product bis(triphenylphosphine)[N-methylimino(2, 6-dimethylphenoxy)methanethiolato] copper(I) (4) is possible. Crystal data for 4: triclinic , a = 10.088(2) Angstrom, b = 11.302(1) Angstrom, c = 17.990(2) Angstrom, alpha = 94.06(1)degrees, beta = 95.22(2)degrees, gamma = 103.94(1)degrees, Z = 2, V = 1974.4(7) Angstrom(3), R = 0.0361. In the presence of of PPh(3), the insertion reaction becomes reversible. This allows the exchange of the heterocumulene MeNCS or the aryloxy group in these molecules with another heterocumulene or a phenol, respectively, when catalytic amounts of PPh(3) are added. Oligomers with exchanged heterocumulmes and phenols could be characterized by independent synthesis.

Flow behavior of LDPE and its blends with LLDPE I and II: A comparative study

Studies on melt rheological properties of blends of low density polyethylene (LDPE) with selected grades of linear low density polyethylene (LLDPE), which differ widely in their melt flow indices, are reported, The data obtained in a capillary rheometer are presented to describe the effects of blend composition and shear rate on flow behavior index, melt viscosity, and melt elasticity. In general, blending of LLDPE I that has a low melt flow index (2 g/10 min) with LDPE results in a decrease of its melt viscosity, processing temperature, and the tendency of extrudate distortion, depending on blending ratio. A blending ratio around 20-30% LLDPE I seems optimum from the point of view of desirable improvement in processability behavior. On the other hand, blending of LLDPE II that has a high melt flow index (10 g/10 min) with LDPE offers a distinct advantage in increasing the pseudoplasticity of LDPE/LLDPE II blends.

A thermal molecular migration in the solid-state - structures of isomeric 5-amino-4-(2,6-dichlorophenyl)-1-(2-nitrophenyl)-1h-1,2,3-triazole (yellow form i) and 4-(2,6-dichlorophenyl)-5-(2-nitroanilino)-2h-1,2,3-triazole (red form-ii), c14h9cl2n5o2

Yellow form (I): Mr= 350.09, monoclinic, P2Jn, Z--4, a=9.525(1), b=14.762(1), c= 11.268(1),/t, fl= 107.82 (1) o , V= 1508.3 A 3 , Din(flotation in aqueous KI)= 1.539 (2), D x= 1.541 (2) g cm -3, #(Cu Ka, 2 = 1.5418 A) = 40.58 cm -~, F(000) = 712, T= 293 K, R = 8.8% for 2054 significant refections. Red form (II): Mr= 350.09, triclinic, Pi, Z=2, a=9.796(2), b= 10.750 (2), c= 7.421 (1)A, a= 95.29 (2), fl= 0108-2701/84/111901-05501.50 70.18 (1), y = 92-.76 (2) °, V= 731.9 A 3, Din(flotation in KI) = 1.585 (3), D x = 1.588 (3) g cm -3, ~t(Cu Ka, 2 = 1.5418/~) = 40.58 cm -1, F(000) = 356, T=293 K, R = 5.8% for 1866 significant reflections. There are no unusual bond distances or angles. The triazole and two phenyl rings are planar. On the basis of packing considerations the possibility of intermolecular interactions playing a role in the reactivity of the starting material is ruled out.

Absorption of intense electromagnetic beams in a magnetoplasma

The multiphoton inverse bremsstrahlung absorption of two intense electromagnetic beams passing through a magnetized plasma is studied. The rate of absorption of electromagnetic energy by the electrons is calculated by deriving a kinetic equation for the electrons. It is found that the absorption enhances when the frequency of one electromagnetic beam is more, and that of the other electromagnetic beam is less, than the electron-cyclotron frequency. A possible application to extragalactic radio sources is discussed.

Influence of Elastic-Constants on Mode-I Stress-Intensity Factors in 3-Dimensional Crack Problems

Plates with V-through edge notches subjected to pure bending and specimens with rectangular edge-through-notches subjected to combined bending and axial pull were investigated (under live-load and stress-frozen conditions) in a completely nondestructive manner using scattered-light photoelasticity. Stress-intensity factors (SIFs) were evaluated by analysing the singular stress distributions near crack-tips. Improved methods are suggested for the evaluation of SIFs. The thickness-wise variation of SIFs is also obtained in the investigation. The results obtained are compared with the available theoretical solutions.

On the shear deformation theory for dynamic analysis of beams

Timoshenko's shear deformation theory is widely used for the dynamical analysis of shear-flexible beams. This paper presents a comparative study of the shear deformation theory with a higher order model, of which Timoshenko's shear deformation model is a special case. Results indicate that while Timoshenko's shear deformation theory gives reasonably accurate information regarding the set of bending natural frequencies, there are considerable discrepancies in the information it gives regarding the mode shapes and dynamic response, and so there is a need to consider higher order models for the dynamical analysis of flexure of beams.

Scheme of squares: Part I. Systems formalism for potentiostatic studies

The so-called “Scheme of Squares”, displaying an interconnectivity of heterogeneous electron transfer and homogeneous (e.g., proton transfer) reactions, is analysed. Explicit expressions for the various partial currents under potentiostatic conditions are given. The formalism is applicable to several electrode geometries and models (e.g., semi-infinite linear diffusion, rotating disk electrodes, spherical or cylindrical systems) and the analysis is exact. The steady-state (t→∞) expressions for the current are directly given in terms of constant matrices whereas the transients are obtained as Laplace transforms that need to be inverted by approximation of numerical methods. The methodology employs a systems approach which replaces a system of partial differential equations (governing the concentrations of the several electroactive species) by an equivalent set of difference equations obeyed by the various partial currents.

Structural Response of Partially Fibrous Concrete Beams

The inclusion of fibers into a matrix over only a partial thickness of the beam is regarded as partially fiber reinforcing a beam. This concept is fully invoked in the present investigation. A tensile strain enhancement factor, t, as determined by a direct tension test, forms a convenient engineering parameter that takes care of the influence of the aspect ratio and volume fraction of the given type of fiber. The appropriate thickness of the beam section to be reinforced with fibers is computed using the above parameter. Necessary analytical expressions were developed to compute the moment enhancement factor associated with different values of the parameter, t. The validity of the approach was experimentally demonstrated. Practically similar deflection patterns for fully and partially fibrous sections were observed. The applicability of the method developed in practical situations, such as the design of airfield and highway pavements with fiber conretes, is cited.

Small-amplitude cyclic voltammetry: Part I. A simple fourier synthesis approach

Current-potential relationships are derived for small-amplitude periodic inputs for linear electrochemical systems using a Fourier synthesis procedure. Specific results have been obtained for a triangular potential waveform for two simple model systems.

Left-handed helices for DNA: studies on poly[d(I-C)]

Earlier, we showed that, for the D form (n = 8 and h = 3.03 A, where n is number of nucleotide units per turn and h is height per nucleotide unit) of poly[d(A-T)], both right- and left-handed double helical models are stereochemically satisfactory and give good agreement with the observed fiber diffraction data. It was also noted that the conformations of the right- and left-handed D-DNA models are very similar to those of the right- and left-handed B-DNA models. This observation was consistent with the D leads to B transition in the solid phase. As a continuation of our earlier studies, we have carried out similar experiments with poly[d(I-C)]. We could obtain a crystalline D-form pattern (n = 8, h = 3.13 A) of the fiber at 75% relative humidity (r.h.); the hydrated (r.h. approximately equal to 95%) form of the same fiber gave the classical B-form pattern (n = 10, h = 3.40 A). In the present report, we show that both right- and left-handed double-helical models are consistent with the fiber diffraction data of poly[d(I-C)] in the D-form. Theoretical energy calculations also suggest that the right- and left-handed B- and D-DNA models are almost equally stable. Hence, we conclude that the right- and left-handed double-helical models of poly[d(I-C)] in a given form (B or D) are equally likely and that the fiber diffraction data do not permit discrimination.

Photoelastic parametric studies of mode I stress intensity factors

Results of photoelastic investigations on single edge-notch tension specimens of varying notch angle and crack length are reported. The experimental results of Mode I stress intensity factors are compared with analytical results.

Push-pull ethylenes: the structures of 3-(2-imidazolidinylidene)-2,4-pentanedione (I), C8H12N2O2, and 3-(1,3-dimethyl-2-imidazolidinylidene)-2,4-pentanedione trihydrate (II), C10H16N2O2.3H2O

(I): Mr= 168, triclinic, P1, Z=2, a= 5.596 (2), b = 6.938 (3), c = 10.852 (4) A, ~t= 75.64 (3), fl= 93.44 (3), ),= 95.47 (3) °, V= 406.0A 3, Din= 1.35 (by flotation using carbon tetrachloride and n-hexane), D x= 1.374 Mg m -3, g(Mo Kct, 2 = 0.7107 A) = 1.08 cm -l, _F(000) = 180, T= 293 K. (II): Mr= 250, triclinic, P1, Z= 2, a = 7.731(2), b=8.580(2), c=11.033(3)A, a= 97-66 (2), fl= 98.86 (2), y= 101.78 (2) °, V= 697.5 A 3, D m = 1.18 (by flotation using KI solution), Dx= 1.190Mgm -3, g(MoKa, 2=0.7107A)= 1.02 cm -1, F(000) = 272, T= 293 K. Both structures were solved by direct methods and refined to R = 4.4% for 901 reflexions for (I) and 5.7% for 2001 reflexions for (II). The C=C bond distances are 1.451 (3) A in (I) and 1.468 (3)A in (II), quite significantly longer than the C=C bond in ethylene [1.336 (2).~; Bartell, Roth, Hollowell, Kuchitsu & Young (1965). J. Chem. Phys. 42, 2683-2686]. The twist angle about the C=C bond in (II) is 72.9 (5) ° but molecule (I) is essentially planar, the twist angle being only 4.9 (5) ° .

Synthesis and Reactions of Binuclear Diolefin Rhodium(I) Compounds bridged by Nitrogen Heterocycles, Crystal Structure of Dichloro-Di-1,5-Cyclooctadiene(Mu-Pyrazine)-Dirhodium(I) [[Rh(1,5-C8h12)Cl]2(Mu-C4h4n2)]

Binuclear complexes of rhodium(I) of the type [(dien)(X)Rh(μ-N-N)Rh(X)(dien)] (dien = 1,5-cyclooctadiene or norbornadiene; N-N = pyrazine, 4,4′-bipyridine or Phenazine and X = Cl or Br) with bridging heterocycles have been isolated and their reactions with carbon monoxide, 2,2′-bipyridine and 1,10-phenanthroline investigated. The crystal structure of [(COD)(Cl)Rh(μ-pyrazine)Rh(Cl)(COD)] has been determined.

Anisotropic gaussian beams

Anisotropic gaussian beams are obtained as exact solutions to the parabolic wave equation. These beams have a quadratic phase front whose principal radii of curvature are non-degenerate everywhere. It is shown that, for the lowest order beams, there exists a plane normal to the beam axis where the intensity distribution is rotationally symmetric about the beam axis. A possible application of these beams as normal modes of laser cavities with astigmatic mirrors is noted.