Reactivity Of Pph3 Toward Ruiiruiiicl(O2car)4 - Syntheses, Molecular-Structures, And Spectroscopic And Electrochemical Properties Of Ruiiruiii(Oh2)Cl(Mecn)(O2car)4(Pph3)2 And Ruii2(Oh2)(Mecn)2(O2car)4(Pph3)2

By the reaction of Ru2Cl(O2CAr)4 (1) and PPh3 in MeCN-H2O the diruthenium(II,III) and diruthenium(II) compounds of the type Ru2(OH2)Cl(MeCN)(O2CAr)4(PPh3)2 (2) and Ru2(OH2)(MeCN)2(O2CAr)4(PPh3)2 (3) were prepared and characterized by analytical, spectral, and electrochemical data (Ar is an aryl group, C6H4-p-X; X = H, OMe, Me, Cl, NO2). The molecular structure of Ru2(OH2)Cl(MeCN)(O2CC6H4-p-OMe)4(PPh3)2 was determined by X-ray crystallography. Crystal data are as follows: triclinic, P1BAR, a = 13.538 (5) angstrom, b = 15.650 (4) angstrom, c = 18.287 (7) angstrom, alpha = 101.39 (3)-degrees, beta = 105.99 (4)-degrees, gamma = 97.94 (3)-degrees, V = 3574 angstrom 3, Z = 2. The molecule is asymmetric, and the two ruthenium centers are clearly distinguishable. The Ru(III)-Ru(II), Ru(III)-(mu-OH2), and Ru(II)-(mu-OH2) distances and the Ru-(mu-OH2)-Ru angle in [{Ru(III)Cl(eta-1-O2CC6H4-p-OMe)(PPh3)}(mu-OH2)(mu-O2CC6H4-p-OMe)2{Ru(II)(MeCN)(eta-1-O2CC6H4-p-OMe)(PPh3)}] are 3.604 (1), 2.127 (8), and 2.141 (10) angstrom and 115.2 (5)-degrees, respectively. The compounds are paramagnetic and exhibit axial EPR spectra in the polycrystalline form. An intervalence transfer (IT) transition is observed in the range 900-960 nm in chloroform in these class II type trapped mixed-valence species 2. Compound 2 displays metal-centered one-electron reduction and oxidation processes near -0.4 and +0.6 V (vs SCE), respectively in CH2Cl2-TBAP. Compound 2 is unstable in solution phase and disproportionates to (mu-aquo)diruthenium(II) and (mu-oxo)diruthenium(III) complexes. The mechanistic aspects of the core conversion are discussed. The molecular structure of a diruthenium(II) compound, Ru2(OH2)(MeCN)2(O2CC6H4-p-NO2)4(PPh3)2.1.5CH2Cl2, was obtained by X-ray crystallography. The compound crystallizes in the space group P2(1)/c with a = 23.472 (6) angstrom, b = 14.303 (3) angstrom, c = 23.256 (7) angstrom, beta = 101.69 (2)-degrees, V = 7645 angstrom 3, and Z = 4. The Ru(II)-Ru(II) and two Ru(II)-(mu-OH2) distances and the Ru(II)-(mu-OH2)-Ru(II) angle in [{(PPh3)-(MeCN)(eta-1-O2CC6H4-p-NO2)Ru}2(mu-OH2)(mu-O2CC6H4-p-NO2)2] are 3.712 (1), 2.173 (9), and 2.162 (9) angstrom and 117.8 (4)-degrees, respectively. In both diruthenium(II,III) and diruthenium(II) compounds, each metal center has three facial ligands of varying pi-acidity and the aquo bridges are strongly hydrogen bonded with the eta-1-carboxylato facial ligands. The diruthenium(II) compounds are diamagnetic and exhibit characteristic H-1 NMR spectra in CDCl3. These compounds display two metal-centered one-electron oxidations near +0.3 and +1.0 V (vs SCE) in CH2Cl2-TBAP. The overall reaction between 1 and PPh3 in MeCN-H2O through the intermediacy of 2 is of the disproportionation type. The significant role of facial as well as bridging ligands in stabilizing the core structures is observed from electrochemical studies.

Reactivity with hydrogen of pure iron oxide and of iron oxides doped with oxides of Mn, Co, Ni and Cu

Using dynamic TG in H2, X-ray powder diffraction and Mössbauer Spectroscopy the reactivities fot hydrogen reduction of Fe2O3 prepared at different temperatures, Fe2O3 doped with oxides of Mn, Co, Ni and Cu prepared at 300DaggerC from nitrate precursors and intermediate spinels derived from above samples during reduction have been explored. The reactivity is higher for finely divided Fe2O3 prepared at 250DaggerC. The reduction is retarded by Mn, marginally affected by Co and accelerated by Ni and Cu, especially at higher (5 at.%) dopant concentration. These reactivities confirmed also by isothermal experiments, are ascribed to the nature of disorder in the metastable intermediate spinels and to hydrogen rsquospill overrsquo effects.

Reduction In Metal-Mold Reactivity In Titanium Castings Through The Use Of Sodium Aluminate As Binder In Zircon Sand Molds

The present work is aimed at evaluating an alternative moulding system, namely, sodium aluminate bonded zircon sand mould and assess its suitability in relation to the much studied sodium silicate bonded zircon sand moulding system. It is described in the study presented here that with regard to metal - mould reaction, sodium aluminate bonded zircon sand mould system is a superior viable system as compared to sodium silicate bonded zircon moulding system at mould firing temperatures of 873 - 1473 K.

Analysis of continuum using boundary compatibility conditions of integrated force method

Static and vibration problems of an indeterminate continuum are traditionally analyzed by the stiffness method. The force method is more or less non-existent for such problems. This situation is primarily due to the incomplete state of development of the compatibility conditions which are essential for the analysis of indeterminate structures by the flexibility method. The understanding of the Compatibility Conditions (CC) has been substantially augmented. Based on the understanding of CC, a novel formulation termed the Integrated Force Method (IFM) has been established. In this paper IFM has been extended for the static and vibration analyses of a continuum. The IFM analysis is illustrated taking three examples: 1. (1) rectangular plate in flexure 2. (2) analysis of a cantilevered dam 3. (3) free vibration analysis of a beam. From the examples solved it is observed that the force response of an indeterminate continuum with mixed boundary conditions can be generated by IFM without any reference to displacements in the field or on the boundary. Displacements if required can be calculated by back substitution.

Allergenic Cross-Reactivity between Parthenium and Ragweed Pollen Allergens

Cross-reactivity of allergens from the pollen of the Compositae weeds, Parthenium hysterophorus (American feverfew) and Ambrosia (ragweed), in 2 groups of patients with different geographic distributions was studied. Parthenium-sensitive Indian patients, who were never exposed to ragweed, elicited positive skin reactions with ragweed pollen extracts. A significant correlation in the RAST scores of Parthenium and ragweed-specific IgE was observed with the sera of Parthenium and ragweed-sensitive Indian and US patients, respectively. RAST inhibition experiments demonstrated that the binding of IgE antibodies in the sera of ragweed-sensitive patients to short (Wl) and giant (W3) ragweed allergen discs could be inhibited by up to 94% by Parthenium pollen extracts. Similar inhibition (up to 82%) was obtained when the sera of Parthenium rhinitis patients were incubated with ragweed allergen extracts. A dose-dependent proliferation of lymphocytes from a Parthenium-sensitive rhinitis patient with elevated levels of both Parthenium and ragweed-specific IgE was observed when incubated with Parthenium and ragweed pollen extracts. A 1.6-fold higher proliferation, however, was observed with Parthenium pollen extract at a concentration of 100 µg/ml. These results suggest that shared epitopes present on Parthenium and ragweed pollen allergens are recognized by both Indian and US patients sensitized by exposure to Parthenium and ragweed pollen, respectively. The high degree of cross-reactivity between Parthenium and ragweed pollen allergens suggests that individuals sensitized to Parthenium may develop type-I hypersensitivity reactions to ragweed and vice versa when they travel to regions infested with the weed to which they had not been previously exposed.

Molecular expression for dielectric friction on a rotating dipole: Reduction to the continuum theory

Recently we presented a microscopic expression for dielectric friction on a rotating dipole. This expression has a rather curious structure, involving the contributions of the transverse polarization modes of the solvent and also of the molecular length scale processes. It is shown here that under proper limiting conditions, this expression reduces exactly to the classical continuum model expression of Nee and Zwanzig [J. Chem. Phys. 52, 6353 (1970)]. The derivation requires the use of the asymptotic form of the orientation‐dependent total pair correlation function, the neglect of the contributions of translational modes of the solvent, and also the use of the limit that the size of the solvent molecules goes to zero. Thus, the derivation can be important in understanding the validity of the continuum model and can also help in explaining the results of a recent computer simulation study of dielectric relaxation in a Brownian dipolar lattice.

Reactivity of pyridinium poly(hydrogen fluoride) towards silicon tetrachloride, trichlorosilane and tris(amino)silanes

The reaction of silicon tetrachloride (SiCl4), trichlorosilane (HSiCl3) and tris(amino)silanes[(R2N)3SiH] with pyridinium poly(hydrogen fluoride) (PPHF) gives rise to hexafluorosilicatesalts in good yields. They have been characterized as pyridinium hexafluorosilicate(C5H5NH)2SiF6 (in the case of SiCl4 and HSiCl3) and the corresponding dialkyl ammoniumhexafluorosilicate (R2NH2)2SiF6 salts [for tris(amino)silanes] (where R2N=pyrrolidino,piperidino, hexamethyleneimino, morpholino, N-methylpiperazino and diethylamino). Theinteresting features of these reactions are the cleavage of Si---Cl, Si---H and Si---N bondsat room temperature by PPHF and fluorination of the silicon moiety to a hexa-coordinateddoubly charged anionic species. These compounds have been characterized by NMR (1H,29Si, 19F) and IR spectroscopy, and by chemical analysis.

Synthesis, Reactivity, Structural Aspects, and Solution Dynamics of Cyclopalladated Compounds of N,N `,N `'-Tris(2-anisyl)guanidine

N,N',N `'-Tris(2-anisyl)guanidine, (ArNH)(2)C=NAr (Ar = 2-(MeO)C6H4), was cyclopallaclated with Pd(OC(O)R)(2) (R = Me, CF3) in toluene at 70 degrees C to afford palladacycles Pd{kappa(2)(C,N)-C6H3-(OMe)-3(NHC(NHAr)(=NAr))-2}(mu-OC(O)R)](2)(R = Me (1a) and CF3 (1b)) in 87% and 95% yield, respectively. Palladacycle 1a was subjected to a metathetical reaction with LiBr in aqueous ethanol at 78 degrees C to afford palladacycle Pd{kappa(2)(C,N)-C6H3(OMe)-3(NHC(NHAr)(=NAr))-2}(mu-Br)](2) (2) in 90% yield. Palladacycle 2 was subjected to a bridge-splitting reaction with Lewis bases in CH2Cl2 to afford the monomeric palladacycles Pd{kappa(2)(C,N)-C6H3(OMe)-3(NHC(NHAr)(=NAr))-2}Br(L)] (L = 2,6-Me2C5H3N (3a), 2,4-Me2C5H3N (3b), 3,5-Me2C5H3N (3c), XyNC (Xy = 2,6-Me2C6H3; 4a), (BuNC)-Bu-t (4b), and PPh3 (5)) in 87-95% yield. Palladacycle 2 upon reaction with 2 equiv of XyNC in CH2Cl2 afforded an unanticipated palladacycle, Pd{kappa(2)(C,N)-C(=NXy)(C6H3(OMe)-4)-2(N=C-(NH Ar)(2))-3} Br(CNXy)] (6) in 93% yield, and the driving force for the formation of 6 was ascribed to a ring contraction followed by amine-imine tautomerization. Palladacycles 1 a,b revealed a dimeric transoid in-in conformation with ``open book'' framework in the solid state. In solution, 1 a exhibited a fluxional behavior ascribed to the six-membered ``(C,N)Pd'' ring inversion and partly dissociates to the pincer type and kappa(2)-O,O'-OAc monomeric palladacycles by an anchimerically assisted acetate cleavage process as studied by variable-temperature H-1 NMR data. Palladacycles 3a,b revealed a unique trans configuration around the palladium with lutidine being placed trans to the Pd-C bond, whereas cis stereochemistry was observed between the Pd-C bond and the Lewis base in 4a (as determined by X-ray diffraction data) and 5 (as determined by P-31 and C-13 NMR data). The aforementioned stereochemical difference was explained by invoking relative hardness/softness of the donor atoms around the palladium center. In solution, palladacycles 3a-c exist as a mixture of two interconverting boat conformers via a planar intermediate without any bond breaking due to the six-membered ``(C,N)Pd'' ring inversion, whereas palladacycles 4a,b and 5 exist as a single isomer, as deduced from detailed H-1 NMR studies.

Photobehavior of crystalline 4-styrylcoumarin dimorphs: structure-reactivity correlations

4-Styrylcoumarin crystallizes from chloroform and hexane mixture in two morphologically different modifications. The monoclinic form (needles, P2(1)/c) undergoes stereospecific photodimerization producing anti head-to-tail dimer across pyrone double bond, whereas the triclinic modification (prisms, P ($) over bar 1) dimerizes yielding photodimer of the same configuration, but across styrenic double bond. Single crystal X-ray analyses of the dimorphs reveal the packing differences permitting rationalization of the regio- and stereochemistry of the photoproducts. The significantly low dimer yield from the prismatic crystals is rationalized.

Reactivity and catalytic activity of layered YBA2CU3O7-delta (123) type defect perovskites

The chemical modifications of structure, reactivity and catalytic properties of layered triple perovskite oxides, related to the YBa2Cu3O7-delta (123) system, have been briefly reviewed. These oxides form a versatile family of materials with wide-ranging chemical and physical properties. The multiple sites available for chemical doping, and the ability to reversibly intercalate oxygen at the defect sites have rendered these oxides important model systems in the area of oxide catalysis. An attempt has been made to comprehend the hitherto known catalytic reactions and correlate them to various factors like structure, oxygen diffusional limitations, different geometries adopted by various substituents, oxidative non-stoichiometry and activation energy for oxygen desorption. In particular, results on the enhanced catalytic activity of cobalt-substituted 123 oxide systems towards the selective catalytic oxidation of ammonia to nitric oxide and carbon monoxide to carbon dioxide are presented.

Studies in crystal engineering: structure�reactivity correlations of substituted styrylcoumarins and related systems

The solid state photochemical behaviour of 7-hydroxy-4-styrylcoumarin 1 and several of its derivatives and analogues has been investigated. All the compounds with the exception of 7-methoxy-4-styrylcoumarin 2 are photolabile and yield anti-HT dimers. It has been observed that chloro substitution in the systems studied does not lead to the expected beta-packing mode. The photobehaviour of 1 and 2 has been correlated with their crystal structures. Reasons for alpha-packing have been examined. The systematics in the arrangement of the carbonyl group and phenyl group of the close neighbours in the crystals of 1, 2 and a few other cases are presented.

Modification of photochemical reactivity on formation of inclusion complexes: photorearrangement of benzyl phenyl ethers and methyl phenoxyacetates

The photorearrangement of benzyl phenyl ethers and methyl phenoxyacetates was investigated in methanol and in complexes with cyclodextrin in both the solid state and aqueous solutions. Irradiation in cyclodextrin media leads to a large change in product distribution with a very significant ortho selectivity different from that found in methanol where the reaction is non-selective. For meta-substituted ethers and phenoxyacetates, an impressive regioselectivity between the two ortho-rearranged isomers is observed and this is significantly enhanced by increasing the substituent chain length which acts as a spacer to induce a tight fit between the host and the guest. The observed results are rationalized on the basis of specific orientations of the unsubstituted and meta-substituted ethers and phenoxyacetates in the cyclodextrin cavity.

Reactivity Of Pph3 Toward Ru2cl(O2cme)4 - Synthesis And X-Ray Crystal-Structure Of [Ru(O2cme)(Mecn)2(Pph3)2](Clo4)

A new ruthenium(II) complex of the type [Ru(O2CMe)(MeCN)2(PPh3)2](CiO4) (1) has been isolated from a reaction between Ru2Cl(O2CMe), and PPh3 in MeCN followed by the addition of NaClO4. The structure of 1 is determined by single crystal X-ray studies. The crystal belongs to the monoclinic space group C2/m with the following unit cell dimensions for the C42H39N2O6P2ClRu(M = 866.15): a = 23.295(1)angstrom, b = 23.080(1)angstrom, c = 9.159(1)angstrom, beta = 107.32(1)-degrees, V = 4701(1)angstrom3, Z = 4, D(c) = 1.224 gcm-3, lambda(Mo - K-alpha) = 0.7107 angstrom, mu(Mo - K-alpha) = 4.09 cm-1, T = 293K, R = 0.081 (R(w) = 0.094) for 2860 reflections with I greater-than-or-equal-to 3-sigma(I) and g = 0.015853. In the complex cation, the symmetry about the metal centre is essentially octahedral showing the presence of a chelating acetato, two cis-oriented MeCN and two trans-disposed PPh3 ligands. The mechanistic aspects of the core cleavage reaction are discussed.