Mechanism of the cobalt oxazoline palladacycle (COP)-catalyzed asymmetric synthesis of allylic esters

The catalytic enantioselective S(N)2' displacement of (Z)-allylic trichloroacetimidates catalyzed by the palladium(II) complex [COP-OAc](2) is a broadly useful method for the asymmetric synthesis of chiral branched allylic esters. A variety of experiments aimed at elucidating the nature of the catalytic mechanism and its rate- and enantiodetermining steps are reported. Key findings include the following: (a) the demonstration that a variety of bridged-dipalladium complexes are present and constitute resting states of the COP catalyst (however, monomeric palladium(II) complexes are likely involved in the catalytic cycle); (b) labeling experiments establishing that the reaction proceeds in an overall antarafacial fashion; (c) secondary deuterium kinetic isotope effects that suggest substantial rehybridization at both C1 and C3 in the rate-limiting step; and (d) DFT computational studies (B3-LYP/def2-TZVP) that provide evidence for bidentate substrate-bound intermediates and an anti-oxypalladation/syn-deoxypalladation pathway. These results are consistent with a novel mechanism in which chelation of the imidate nitrogen to form a cationic palladium(II) intermediate activates the alkene for attack by external carboxylate in the enantiodetermining step. Computational modeling of the transition-state structure for the acyloxy palladation step provides a model for enantioinduction.     

Six‐coordinate Co2+ with imidazole,NH3, and H2O ligands: Approaching spin crossover

Octahedral, six‐coordinate Co²⁺ can exist in two spin states: S = 3/2 and S = 1/2. The difference in energy between high spin (S = 3/2) and low spin (S = 1/2) is dependent on both the ligand mix and coordination stereochemistry. B3LYP calculations on combinations of neutral imidazole, NH₃, and H₂O ligands show that low‐spin isomers are stabilized by axial H₂O ligands and in structures that also include trans pairs of equatorial NH₃ and protonated imidazole ligands, spin crossover structures are predicted from spin state energy differences. Occupied Co d orbitals from the DFT calculations provide a means of estimating effective ligand strength for homoleptic and mixed ligand combinations. These calculations suggest that in a labile biological system, a spin crossover environment can be created. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Computing the ideal structure of finite semigroups

In this paper algorithms are described for computing the equivalence classes induced by the Green relations on the elements of a finite semigroup.     

External cavity quantum cascade laser for quartz tuning fork photoacoustic spectroscopy of broad absorption features

We demonstrate mid-infrared spectroscopy of large molecules with broad absorption features using a tunable external cavity quantum cascade laser. Absorption spectra for two different Freons are measured over the range 1130-1185 cm(-1) with 0.2 cm(-1) resolution via laser photoacoustic spectroscopy with quartz tuning forks as acoustic transducers. The measured spectra are in excellent agreement with published reference absorption spectra.     

Zur Bestimmung des Adrenalins

Ohne Zusammenfassung     

On hyperbolic once-punctured-torus bundles II: fractal tessellations of the plane

We describe fractal tessellations of the complex plane that arise naturally from Cannon–Thurston maps associated to complete, hyperbolic, once-punctured-torus bundles. We determine the symmetry groups of these tessellations. To our wives, Ardyth and Elena.     

A priori estimate for continuation of the solution of the heat equation in the space variable

Summary Let u(x, t) satisfy the heat equation in a region D in the x−t plane and vanish initially. Let |u|<M₀ in D and |u _i ² |<∈ in D* ⊂ D. Then, in D−D*, |u|< , where B=B(x, t) satisfies O<B<1 and B(x, t) and M₁ are given explicity by simple formulas. The a priori bound is applied to an error analysis of a numerical procedure for continuing solutions of the heat equation in the space variable. Work was performed under the auspices of the U. S. Atomic Energy Commission.     

Classical and weak solutions for one-dimensional pseudo-parabolic equations with typical boundary data

Summary In this paper we consider the pseudo-parabolic equations arising in the filtration of water in media with double porosity and moisture transfer in soil. The existence, uniqueness and stability for both classical and weak solutions are studied.