Unusual monodentate binding mode of 2,2'-dipyridylamine (L) in isomeric trans-(acac)2RuII(L)2, trans-[(acac)2RuIII(L)2]ClO4, and cis-(acac)2RuII(L)2 (acac = acetylacetonate). synthesis, structures, and spectroscopic, electrochemical, and magnetic aspects

The reaction of cis-Ru(acac)2(CH3CN)2 (acac = acetylacetonate) with 2,2'-dipyridylamine (L) in ethanolic medium resulted in facile one-pot synthesis of stable [(acac)2RuIII(L)]ClO4 ([1]ClO4), trans-[(acac)2RuII(L)2] (2), trans-[(acac)2RuIII)L)2]ClO4 ([2]ClO4), and cis-[(acac)2RuII(L)2] (3). The bivalent congener 1 was generated via electrochemical reduction of [1]ClO4. Although in [1]+ the dipyridylamine ligand (L) is bonded to the metal ion in usual bidentate fashion, in 2/[2]+ and 3, the unusual monodentate binding mode of L has been preferentially stabilized. Moreover, in 2/[2]+ and 3, two such monodentate L's have been oriented in the trans- and cis-configurations, respectively. The binding mode of L and the isomeric geometries of the complexes were established by their single-crystal X-ray structures. The redox stability of the Ru(II) state follows the order 1 < 2 < 3. In contrast to the magnetic moment obtained for [1]ClO4, mu = 1.84 muB at 298 K, typical for low-spin Ru(III) species, the compound [2]ClO4 exhibited an anomalous magnetic moment of 2.71 muB at 300 K in the solid state. The variable-temperature magnetic measurements showed a pronounced decrease of the magnetic moment with the temperature, and that dropped to 1.59 muB at 3 K. The experimental data can be fitted satisfactorily using eq 2 that considered nonquenched spin-orbit coupling and Weiss constant in addition to the temperature-independent paramagnetism. [1]ClO4 and [2]ClO4 displayed rhombic and axial EPR spectra, respectively, in both the solid and the solution states at 77 K.     

A new kinetic model for bulk polymerization of vinyl chloride based on two-phase hypothesis

A kinetic model has been developed for the bulk polymerization of vinyl chloride using Talamini's hypothesis of two-phase polymerization and a new concept of kinetic solubility which assumes that rapidly growing polymer chains have considerably greater solubility than the thermodynamic solubility of preformed polymer molecules of the same size and so can remain in solution even under thermodynamically unfavourable conditions. It is further assumed that this kinetic solubility is a function of chain length. The model yields a rate expression consistent with the experimental data for vinyl chloride bulk polymerization and moreover is able to explain several characteristic kinetic features of this system. Application of the model rate expression to the available rate data has yielded 2.36 × 10⁸l mol^?1 sec^?1 for the termination rate constant in the polymer-rich phase; as expected, this value is smaller than that reported for homogenous polymerization by a factor of 10–30.     

A facile one‐pot synthesis of novel substituted 1,2,3,4‐tetrahydropyrimidine,part 2: Synthesis of 1‐(aralkyl/aryl)‐3‐(alkyl/aralkyl/aryl)‐5‐aroyl‐1,2,3,4‐tetrahydropyrimidines

1‐(Aralkyl/aryl)‐3‐(alkyyaralkyl)‐5‐aroyl‐1,2,3,4‐tetrahydropyrimidines ( 2a‐c ) have been synthesized by dethiomethylation of 5‐aroyl‐6‐methylthio‐1,2,3,4‐tetrahydropyrimidines ( 1a‐c ). An alternative one‐pot synthetic strategy has been developed for the title compounds 2a‐t by the reaction of enaminones 3 with pri mary amine and formaldehyde in refluxing methanol in good yields.     

Complex series [Ru(tpy)(dpk)(X)]n+ (tpy = 2,2':6',2''-terpyridine; dpk = 2,2'-dipyridyl ketone; X = Cl-, CH3CN, NO2(-), NO+, NO*, NO-): substitution and electron transfer, structure, and spectroscopy

The complex framework [Ru(tpy)(dpk)]2+ has been used to study the generation and reactivity of the nitrosyl complex [Ru(tpy)(dpk)(NO)]3+ ([4]3+). Stepwise conversion of the chloro complex [Ru(tpy)(dpk)(Cl)]+ ([1]+) via [Ru(tpy)(dpk)(CH3CN)]2+ ([2]2+) and the nitro compound [Ru(tpy)(dpk)(NO2)]+ ([3]+) yielded [4]3+; all four complexes were structurally characterized as perchlorates. Electrochemical oxidation and reduction was investigated as a function of the monodentate ligand as was the IR and UV-vis spectroscopic response (absorption/emission). The kinetics of the conversion [4]3+/[3]+ in aqueous environment were also studied. Two-step reduction of [4]3+ was monitored via EPR, UV-vis, and IR (nu(NO), nu(CO)) spectroelectrochemistry to confirm the {RuNO}7 configuration of [4]2+ and to exhibit a relatively intense band at 505 nm for [4]+, attributed to a ligand-to-ligand transition originating from bound NO-.     

Delineating incoherent non-Markovian dynamics using quantum coherence

We introduce a method of characterization of non-Markovianity using coherence of a system interacting with the environment. We show that under the allowed incoherent operations, monotonicity of a valid coherence measure is affected due to non-Markovian features of the system–environment evolution. We also define a measure to quantify non-Markovianity of the underlying dynamics based on the non-monotonic behavior of the coherence measure. We investigate our proposed non-Markovianity marker in the behavior of dephasing and dissipative dynamics for one and two qubit cases. We also show that our proposed measure captures the back-flow of information from the environment to the system and compatible with well known distinguishability criteria of non-Markovianity.     

Neighbouring group effect on the kinetics of acetalisation of poly(vinyl alcohol)

A kinetic model for acetalisation of poly(vinyl alcohol) (PVOH) involving a neighbouring group effect has been developed using a statistical approach. Assuming that the acetalisation proceeds irreversibly, an effectiveness factor (defined as the ratio of the concentration of reactable hydroxyl groups to the total concentration of hydroxyl groups of the polymer) has been obtained as a function of conversion. When the effect of neighbouring groups on the reactivity of OH groups is neglected, the model predicts a maximum attainable conversion of 87% which compares well with that postulated by Flory for irreversible acetalisation. Possibilities of conversions > 87%, as reported by some investigators, are discussed. Flory accounted for such higher conversions by postulating reversibility of the acetalisation. Experimental studies reported in the literature, however, indicate the acetalisation to be essentially irreversible. It is shown here that the present model, with the inclusion of the neighbouring group effect, can account for such higher conversions even for irreversible acetalisation of PVOH.     

Continuum thermodynamic formulation of models for electromagnetic thermoinelastic solids with application in electromagnetic metal forming

The purpose of this work is the formulation and application of a continuum thermodynamic approach to the phenomenological modeling of a class of engineering materials which can be dynamically formed using strong magnetic fields. This is carried out in the framework of a thermodynamic, internal-variable-based formulation in which the deformation, temperature and magnetic fields are in general coupled. This coupling takes the form of the Lorentz force as an additional supply of momentum, and the electromotive power as an additional supply of energy, in the material. In the current approach, the basic thermomechanical field relations for mass, momentum and moment of momentum are obtained from the total energy balance via invariance, and completed by Maxwells field equations. The constitutive formulation is based on the exploitation of the Müller-Liu entropy principle, here for the case of isotropic thermoelastic, viscoplastic material behaviour. The resulting reduced constitutive and field relations and restrictions are then applied to the modeling and simulation of high-speed electromagnetic forming of metal tubes and sheet metal. In this context, scaling arguments show that, over the relevant length- and timescales of engineering interest, the evolution of the magnetic field is diffusive in nature, and thermal conduction is negligible. Comparison of the simulation and experimental results for the final sheet metal form shows very good agreement.Received: 16 March 2004, Accepted: 6 May 2004, Published online: 17 September 2004PACS: 46.05. + b, 46.25.Hf, 46.35 + z Correspondence to: B. Svendsen     

Fabrication of Au-Pd core-shell heterostructures with systematic shape evolution using octahedral nanocrystal cores and their catalytic activity

By using octahedral gold nanocrystals with sizes of approximately 50 nm as the structure-directing cores for the overgrowth of Pd shells, Au-Pd core-shell heterostructures with systematic shape evolution can be directly synthesized. Core-shell octahedra, truncated octahedra, cuboctahedra, truncated cubes, and concave cubes were produced by progressively decreasing the amount of the gold nanocrystal solution introduced into the reaction mixture containing cetyltrimethylammonium bromide (CTAB), H(2)PdCl(4), and ascorbic acid. The core-shell structure and composition of these nanocrystals has been confirmed. Only the concave cubes are bounded by a variety of high-index facets. This may be a manifestation of the release of lattice strain with their thick shells at the corners. Formation of the [CTA](2)[PdBr(4)] complex species has been identified spectroscopically. Time-dependent UV-vis absorption spectra showed faster Pd source consumption rates in the growth of truncated cubes and concave cubes, while a much slower reduction rate was observed in the generation of octahedra. The concave cubes and octahedra were used as catalysts for a Suzuki coupling reaction. They can all serve as effective and recyclable catalysts, but the concave cubes gave higher product yields with a shorter reaction time attributed to their high-index surface facets. The concave cubes can also catalyze a wide range of Suzuki coupling reactions using aryl iodides and arylboronic acids with electron-donating and -withdrawing substituents.     

Solutions of Yang's EuclideanR-gauge equations and self-duality

Under some assumptions and transformations of variables, Yang's equations forR-gauge fields on Euclidean space lead to conformally invariant equations permitting one to obtain infinitely many other solutions from any solution of these conformally invariant equations. These conformally invariant equations closely resemble the mathematically interesting generalized Lund-Regge equations. Some exact solutions of these conformally in variant equations are obtained. Except for some singular situations, these solutions are self-dual.