A pyrimidine thiolate Rh(I) complex: structure, bonding and one-dimensional interactions in solid and in solution

The reaction of [Rh(micro-Cl)(COD)]2 with 4,6-dimethyl-pyrimidinethiolate (Me2-pymt) and subsequent substitution of COD by CO yields [Rh(Me2-pymt)(CO)2]. The stacking pattern found in this compound is in contradiction with previously studied comparable square-planar complexes of type d8-[M(chelate)(monodentate)2] in which each ligand has different pi-acidic character. A theoretical study of the intermolecular interactions and conformation of the title compound has been carried out, combining semi-empirical band calculations on the real chains and ab initio(MP2 level) calculations on a model dimer. The combination of electronic and steric effects determines the rotation of the successive monomers and the deviation from linearity of the one-dimensional stacks. Its behaviour in solution is also special, developing a blue colour and forming micelles, when adding water to acetone solutions.     

Solid-phase synthesis of the cyclic lipononadepsipeptide [N-Mst(Ser1), d-Ser4, L-Thr6, L-Asp8, L-Thr9]syringotoxin

An optimized solid-phase strategy for the preparation of the cyclic lipononadepsipeptide [N-Mst(L-Ser1), D-Ser4, L-Thr6, L-Asp8, L-Thr9]syringotoxin is reported. The strategy is based on the use of a mild orthogonal protection scheme and the incorporation of the nonproteinogenic amino acid (Z)-Dhb into the peptide chain as the dipeptide Fmoc-Thr(tBu)-(Z)-Dhb-OH. The didehydrodipeptide was synthesized by a water-soluble carbodiimide-induced beta-elimination of a protected dipeptide containing a residue of Thr with its free hydroxy side chain unprotected.     

A density functional theory study of the gas-phase elimination reactions of 4-arylideneimino-1,2,4-triazol-3(2H )-ones and their 3(2H )-thione analogues

Theoretical studies on the thermolysis in the gas phase of 4-arylideneimino-1,2,4-triazol-3(2H)-ones and 4-arylideneimino-1,2,4-triazol-3(2H)-thiones were carried out using density functional theory methods, at the B3LYP/6-31G(d) and B3LYP/6-311+G(2d,p) levels of theory. The proposed reaction mechanism occurs in one step, leading to the formation of 3-hydroxy-(2H)-1,2,4-triazole or 3-mercapto-(2H)-1,2,4-triazole and a 4-substituted benzonitrile, via a six-membered cyclic transition state. The progress of the reactions was followed by means of the Wiberg bond indices. The results indicate that the transition states have character intermediate between reactants and products, and the calculated synchronicities show that the reactions are slightly asynchronous, in the case of triazolones, and show a higher asynchronicity in the case of triazolthiones. The bond-breaking processes are slightly more advanced than the bond-forming ones, indicating a small bond deficiency in the transition states. Kinetic and activation parameters for the reactions studied have been calculated and compared with available experimental data.From the Proceedings of the 28th Congreso deQuímicos Teóricos de Expresión Latina (QUITEL 2002)     

Toward inorganic electrides

Electrides are materials in which alkali metals (Li through Cs) ionize to form bound alkali cations and "excess" electrons. The electrons reside in large cavities or channels or both in the host lattice. We report here the first synthesis of thermally stable inorganic electrides with cation-to-electron ratios of 1:1 as in organic electrides. Although alkali metal adducts to alumino-silicate zeolites are well known, the cation-to-electron ratio is generally 3:1 or greater because these zeolites contain alkali cations prior to incorporation of the alkali metal. In this work, two pure silica zeolites, ITQ-4and ITQ-7, with pore diameters of approximately 7 A, absorb up to 40 wt % cesium from the vapor phase (even at room temperature). The other alkali metals (except Li) can also be introduced at elevated temperatures. The optical and magnetic properties of the cesium-loaded samples suggest ionization to form Cs+ and e- with substantial electron-spin pairing. The metal-loaded samples are stable to at least 100 degrees C and are able to reduce small aromatic molecules such as benzene and naphthalene to the radical anions within the pores of the zeolite.     

Random Activations in Primal-Dual Splittings for Monotone Inclusions with a Priori Information

Journal of Optimization Theory and Applications - In this paper, we propose a numerical approach for solving composite primal-dual monotone inclusions with a priori information. The underlying a...     

Real analysis related to the Monge-Ampère equation

In this paper we consider a family of convex sets in , , , , satisfying certain axioms of affine invariance, and a Borel measure satisfying a doubling condition with respect to the family The axioms are modelled on the properties of the solutions of the real Monge-Ampère equation. The purpose of the paper is to show a variant of the Calderón-Zygmund decomposition in terms of the members of This is achieved by showing first a Besicovitch-type covering lemma for the family and then using the doubling property of the measure The decomposition is motivated by the study of the properties of the linearized Monge-Ampère equation. We show certain applications to maximal functions, and we prove a John and Nirenberg-type inequality for functions with bounded mean oscillation with respect to

     

Cohomology of the complement of a free divisor

We prove that if is a ``strongly quasihomogeneous" free divisor in the Stein manifold , and is its complement, then the de Rham cohomology of can be computed as the cohomology of the complex of meromorphic differential forms on with logarithmic poles along , with exterior derivative. The class of strongly quasihomogeneous free divisors, introduced here, includes free hyperplane arrangements and the discriminants of stable mappings in Mather's nice dimensions (and in particular the discriminants of Coxeter groups).

     

Arrangements of hyperplanes with property D

We denote by the complement of the complexification of a real arrangement of hyperplanes. It is known that there is a certain technical property, called property D, on real arrangements of hyperplanes such that: if a real arrangement of hyperplanes is simplicial then has property D, and if has property D then is aK(, 1) space. Our main goal is to prove that: if has property D then is simplicial. We also prove that a quasi-simplicial arrangement is always simplicial.     

Self-consistent solutions of the semiclassical Einstein equations with cosmological constant

The general solution to the semiclassical backreaction equation is found for conformally invariant free quantum fields in spatially flat homogeneous and isotropic spacetime with Cosmological constant and with no classical source when the ratio of the renormalisation parameters/=9/4. It contains a two-parameter family of bouncing solutions that avoid the singularity. There are several one-parameter families which do not have particle horizons. The stability of these solutions is investigated and it is found that they are stable when and have different signs. However, when both parameters have the same sign the set of stable solutions is restricted by the condition 0 < < 1/9. In both cases these solutions have a final de Sitter stage.     

Weyl equation in some anisotropic stiff fluid universes

The Weyl equation (massless Dirac equation) is studied in a family of exact solutions of the Einstein equations whose material content is a perfect fluid with stiff equation of state (p=) and which are of Bianchi type I. The field equation is solved exactly for some members of the family.