Theoretical study of unimolecular rearrangements of vinylidenes to acetylenes

The rearrangement of vinylidene to acetylene has been studied in detail by the density functional method, using Becke's three‐parameter exchange functional and the gradient‐corrected functional of Lee, Yang, and Parr. The rearrangement of the anion, as well as that of fluoro‐substituted systems, has also been investigated, in order to determine the effect of fluorine substitution on the activation barrier to the 1,2‐hydrogen shift, as well as the relative migratory aptitudes of hydrogen and fluorine. Natural bond orbital analysis is invoked to gain insight into the mechanisms of the rearrangements. Basis size effects are also discussed, particularly in relation to anionic systems. The need to include diffuse functions in geometry optimizations of anionic systems is reinforced by the present calculations. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Iridodials: enantiospecific synthesis and stereochemical assignment of the pheromone for the golden-eyed lacewing, Chrysopa oculata

1R,2S,5R,8R; 1R,2S,5R,8S; 1S,2S,5R,8R; and 1S,2S,5R,8S-Iridodials have been prepared in five steps from 4aS,7S,7aR and 4aS,7S,7aS-nepetalactones, major components of catnip oil. 1R,2S,5R,8R-Iridodial has been identified as a male-produced male-aggregation pheromone for Chrysopa oculata, the first pheromone of any kind identified for lacewings.     

Synthesis of O,O Ethane Bridged Bis-copper(II) Macrocycles. Selective Enzyme Model for Catecholase Activity

New mononuclear and dinuclear complexes [3-hydroxyethyl-1,3,5,8,11pentaazacyclotridecane]copper(II) (1)/nickel(II) (2) perchlorate and O,O ethane bridged bis-copper(II) (3)/nickel(II) (4) macrocycles have been synthesized and characterized by various spectroscopic techniques, viz. i.r., n.m.r., e.p.r., u.v.–vis. and conductance measurements. Spectral data and conductance measurements reveal that all the complexes are consistent with square-planar geometry and are ionic in nature. The catalytic activity of the dinuclear Cu(II) complex (3) in the presence of pyrocatechol was determined spectrometrically by monitoring the increase of the o-benzoquinone characteristic absorption band at 25,000 cm⁻¹ with respect to time in DMF saturated with molecular oxygen. The kinetic parameters V_max (2.8×10⁻³ M s⁻¹) and K_M (1.4×10⁻³ mm) have been determined by Michaelis–Menten method. Electrochemistry of the dinuclear Cu(II) complex has been studied in the presence of molecular oxygen with pyrocatechol and without pyrocatechol at a scan rate of 0.1 V s⁻¹ by cyclic voltammetry. On addition of pyrocatechol, complex shows a shift in E_pc, E_pa and E_1/2 values indicating the oxidation of substrate (pyrocatechol).     

Mirror image nanostructures

Chiral molecules that self-assemble to form chiral supramolecular structures exhibit interesting structural features reminiscent of tertiary and quaternary structures of proteins and have applications in catalysis and nonlinear optics. Often, these structures are hierarchical, with their chiral structure difficult to interpret on the molecular scale. In this communication, we observe chiral assembling molecules that form well-defined helices with a pitch of 28 nm. We observe the behavior in both R- and S-enantiomers of the molecule, forming mirror image nanostructures. The molecular chirality is determined by the dimethyloctyl alkyl coil of the molecule and is located more than 4 nm from the hydrogen-bonding segment. The nanostructures observed are not hierarchical, which could be a result of the significant separation between the stereocenter and hydrogen-bonding dendron. The subtle structural modification at the periphery of the molecule biases the supramolecular assembly, which is driven primarily by strong hydrogen-bonding and pi-pi stacking interactions.     

Crystallographic evidence of hexacoordination at phosphorus via intramolecular coordination of donor groups on phosphane and phosphane sulphide

The X-ray structure analysis of bis(8-dimethylamino-l-naphthyl)phenylphosphane (3) and of the corresponding sulphide 4 has revealed hexacoordination at phosphorus in both cases, the N … P separations being less than the sum of the van der Waal radii. Furthermore, in both cases the overall geometry corresponds to a distorted bicapped tetrahedron. The optimum geometry calculated for 4 via the program developed by Autodesk (MM + method) suggests that the structure of the molecule is a function not only of steric requirements but also of electronic effects.     

Enantioselective separation on a naturally chiral surface

Kinked-stepped, high Miller index surfaces of metal crystals are chiral and, therefore, exhibit enantiospecific properties. Previous temperature-programmed desorption (TPD) spectra have shown that the desorption energies of R-3-methylcyclohexanone (R-3-MCHO) on the chiral Cu(643)(R) and Cu(643)(S) surfaces are enantiospecific (J. Am. Chem. Soc. 2002, 124, 2384). Here, a comparison of the TPD spectra from Cu(111), Cu(221), Cu(533), Cu(653)(R&S), and Cu(643)(R&S) surfaces reveals that the enantiospecific desorption occurs from the chiral kink sites on the Cu(643) surfaces. Titration of the chiral kink sites with I atoms confirms this assignment of desorption features in the TPD spectra. Finally, the enantiospecific difference in the desorption energies of R- and S-3-MCHO has been used as the basis for demonstration of an enantioselective, kinetic separation of racemic 3-MCHO into its purified components during adsorption and desorption on the Cu(643)(R&S) surfaces.     

Synthesis, spectra and biomimetic properties of copper(II)-copper(II) and copper(II)-zinc(II) binuclear complexes with CuN5 chromophores

X-band electron spin resonance (ESR) and UV-vis spectra of a homobinuclear [(Bipy)2Cu-E-Im-Cu(Bipy)2](BF4)3 and a heterobinuclear [(Bipy)2Cu-E-Im-Zn(Bipy)2](BF4)3 complexes, E-Im=2-ethylimidazolate ion have been described as possible models for superoxide dismutase (SOD). Magnetic moment and ESR spectral measurements of the homobinuclear complex have shown an antiferromagnetic exchange interaction. From pH-dependent ESR and UV-vis spectral measurements studies, these complexes have been found to be stable over 8.5-10.5 pH range. These complexes catalyze the dismutation of superoxide (O2-) at biological pH. All the observations indicate that these complexes act as good possible models for superoxide dismutase.     

Biomimetic reduction of nimesulide with NaBH4 catalyzed by metalloporphyrins

The biomimetic reduction of anti-inflammatory drug, nimesulide (1) with sodium borohydride catalyzed by 5,10,15,20-tetraarylporphyrinatoiron(III) chlorides [TAPFe(III)Cl] has been studied in organic solvents under anaerobic and aerobic conditions.