Reactions of Mixed-Valent Palladium (IV,II) Complexes of Tetradentate Schiff-Bases Involving Bond Isomerization

Reactions of [PdIVB-(AI)2]++ [PdIICl4]-- (i) B-(AI)2 = dianion of N,N'-ethylene-/i-propylene-/n-propylene-bis(acetyl-acetoneimine) with some π-acceptor ligands, aliphatic primary amines and nitrosating reagents have been investigated. In all these reactions except nitrosation, 1:1 adducts having the formula, [PdIVB-(AI)2.X] [PdIICl4] [X = triphenylphosphine (TPP), triphenylarsine (TPA), pyridine (Py), methylamine (CH3NH2) or ethylamine (C2H5NH2)] are obtained. The formation of these complexes is associated with a bond isomerization - from Pd-Cxo-π -allylic bond prevailing in [PdIVB-(AI)2]2+ to PdIV-O bonding.Reaction of (i) with nitrosating reagents reduces PdIV to PdII and subsequently transform the γ-CH group, into an ambidentate isonitroso group (°C = NOH). The latter enters into coordination with PdII by dislodging the already coordinated carbonyl group. Further, selective nitrosation (mono- and dinitrosation) has been carried out by controlling the amount of the nitrosating reagent and the reaction time. The complexes have been characterized by elemental analyses, electrical conductivity, magnetic susceptibility and ir spectral data.

The influence of lone-pair repulsions on C–C bond lengths: a critical evaluation of the experimental and theoretical evidence

X-Ray structural data, as well as semiempirical and ab initio molecular orbital calculations, reveal no systematic and substantial difference between the C–C bond lengths of cis and trans 1,2-diketones. Additional results on various conformations of 1,2-diimines and 1,2-dithiones follow the same pattern. Therefore, lone-pair repulsions cannot be implicated in the observed lengthening of C–C bonds in isatin and several related molecules. Conjugation in these systems occurs peripherally avoiding the participation of the central C–C bond. Negative hyperconjugative interaction between the oxygen lone pairs and the adjacent C–C σ* orbital is suggested to be the principal reason for the relatively long C–C bond in diketones. This effect is found in both the cis and trans conformations.

Macroscopic model of city traffic using bond graph modelling

Modelling of city traffic involves capturing of all the dynamics that exist in real-time traffic. Probabilistic models and queuing theory have been used for mathematical representation of the traffic system. This paper proposes the concept of modelling the traffic system using bond graphs wherein traffic flow is based on energy conservation. The proposed modelling approach uses switched junctions to model complex traffic networks. This paper presents the modelling, simulation and experimental validation aspects.

A2MoTiO7−x (Atriple bond; length as m-dashrare earth or Y): a new series of oxide pyrochlores prepared by topochemical reduction of A2MoTiO8 scheelites

A series of anion-deficient pyrochlore oxides of the formula A2MoTiO7−x (xless-than-or-equals, slant0.5), where Atriple bond; length as m-dashSm, Gd, Tb, Dy, Ho, Er, Lu and Y, has been prepared by reduction of A2MoTiO8 scheelites. The scheelite-to-pyrochlore conversion is reversible, indicating that the reaction is likely to be topochemical. The oxidation states of molybdenum and titanium are most probably Mo(III) and Ti(IV) for the limiting composition of the pyrochlores A2MoTiO6.5. The new pyrochlores are non-metallic and paramagnetic as expected.

Sensitivity of Lau fringes to grating rotation: theoretical analysis

Recently reported experimental results on the rotation sensitivity of Lau fringes to the spatial coherence of the source have been theoretically analyzed and explained on the basis of coherence theory. A theoretical plot of the rotation angle required for the Lau fringes to vanish is obtained as a function of the coherence length of the illumination used in the Lau experiment. The theoretical results compare well with the experimental observations. The analysis as well as the experiment could form the basis for a simple and easy measurement of the coherence length of the illumination in a plane.

A parametric method 3 (PM3) study of trans‐stilbene

We report a comparative modified neglect of diatomic overlap (MNDO), Austin method one (AM1), and parametric method 3 (PM3) study of trans‐stilbene (tS) in its ground, excited (singlet and triplet), and ionic (positive and negative polarons and bipolarons) states. We have also calculated the barrier for ring rotation about the backbone single bond. Our results show that PM3 geometries are superior to MNDO and AM1, at least for tS. PM3 predicts, in contrast with MNDO, AM1 and even ab initio 3‐21G, a coplanar structure for tS, in accordance with recent experimental data. Singlet and triplet energies obtained from heats of formation are in surprisingly good agreement with experimental data.

Conformational Studies of Some Alpha-substituted Acetones CH3COCH2XCH3 Where X=CH2, O Or S And Phenacyl Sulfide

Both semiempirical and ab initio calculations are reported for conformational studies of a series of alpha-substituted acetones CH3COCH2XCH3 where X = CH2, O or S and of phenacyl sulfide PhCOCH2SCH3. For conformational studies in the lowest triplet state of these molecules, the MINDO/3 method was employed in the unrestricted Hartree-Fock frame. Results reveal that rotation around a bond alpha to the carbonyl group is more favourable than that around the beta bond. The preferred conformations in the lowest triplet state are nearly the same as in the ground state.

Is a CImage C quadruple bond possible?

Ab initio computations Predict a minimum for a carbon-carbon quadruple bond in C2. While the computed C-C separation, 1.128 angstrom, fits Pauling's bond order-bond length relationship well, this result is an artifact of the restricted Hartree Fock theory.

Symmetry adaptation of correlated states in the valence bond basis

Symmetry?adapted linear combinations of valence?bond (VB) diagrams are constructed for arbitrary point groups and total spin S using diagrammatic VB methods. VB diagrams are related uniquely to invariant subspaces whose size reflects the number of group elements; their nonorthogonality leads to sparser matrices and is fully incorporated into a binary integer representation. Symmetry?adapated linear combinations of VB diagrams are constructed for the 1764 singlets of a half?filled cube of eight sites, the 2.8 million ??electron singlets of anthracene, and for illustrative S?0 systems.

Microtensile testing of a free-standing Pt-aluminide bond coat

A finite element method (FEM)-based study has been carried out for the design of flat microtensile samples to evaluate tensile properties of Pt-aluminide (PtAl) bond coats. The critical dimensions of the sample have been determined using a two-dimensional elastic stress analysis. In the present testing scheme, the ratio of the dimensions of the holding length to the fillet radius of the sample was found important to achieve failure within the gage length. The effect of gage length and grip head length also has been examined. The simulation predictions have been experimentally verified by conducting microtensile test of an actual PtAl bond coat at room temperature. The sample design and testing scheme suggested in this study have also been found suitable for evaluation of tensile properties at high temperature. (C) 2010 Elsevier Ltd. All rights reserved.

A note on the slow rotation of a disc in a bounded fluid with a surfactant surface layer

A method involving eigenfunction expansion and collocation is employed to solve the axisymmetric problem of a slowly and steadily rotating circular disc in a fluid of finite extent whose surface is covered with a surfactant film. The present method (originally described by Wang (Acta Mech. 94, 97, 1992)) is observed to produce results of practical importance associated with the problem more quickly and more easily than the one used earlier by Shail and Gooden (Int. J. Multiphase Flow 7, 245, 1992). (C) 1994 Academic Press, Inc.