Overcoming challenges in the palladium-catalyzed synthesis of electron deficient ortho-substituted aryl acetonitriles

Highly electron deficient monoaryl, di-aryl and bis-diaryl acetonitriles were effectively synthesized using either a nucleophilic aromatic substitution (NAS) or a palladium-mediated coupling pathway. Synthesis of di-aryl acetonitriles most conveniently proceeded via NAS--palladium-mediated coupling was not required. This reaction, however, results in a product that is more acidic than the reactants. Facile deprotonation of the product prevents efficient formation of the bis-diaryl acetonitrile through a NAS pathway. Thus, palladium-mediated coupling is required to prepare the bis-diaryl acetonitrile efficiently. In the palladium-catalyzed coupling, choice of base and solvent (and thus the counter cation for the benzylic anion nucleophile) is important. Also, choice of the supporting ligand is important, indicating the sensitivity of the reaction to steric and ligand electronic effects.     

Semi‐Markov processes and mobility: A note

For at least twenty‐five years, the concept of the clique has had a prominent place in sociometric and other kinds of sociological research. Recently, with the advent of large, fast computers and with the growth of interest in graph‐theoretic social network studies, research on the definition and investigation of the graph theoretic properties of clique‐like structures has grown. In the present paper, several of these formulations are examined, and their mathematical properties analyzed. A family of new clique‐like structures is proposed which captures an aspect of cliques which is seldom treated in the existing literature. The new structures, when used to complement existing concepts, provide a new means of tapping several important properties of social networks.     

Unusual pulsating states in hydrocarbon-oxygen premixed flames

An unusual type of pulsating state has been observed using a new ignition protocol for heavy hydrocarbon-oxygen premixed flames on a circular porous plug burner. The shape and motion of these states are quasicircular, luminous, pulsating regions of M (M=1, 2, 3, or 4) lobes that increase in size as the flame propagates outward. As the lobes expand, they break apart near their midpoints and form counterpropagating spiral-like arms. These spiral arms rotate, "collide" with arms generated by adjacent lobes, and are extinguished. We will describe the unusual characteristics of the dynamics of these states.     

Enhancement of second harmonic generation efficiency: Growth and characterization of magnesium(II)-doped tetrakis(thiourea)nickel(II) chloride crystals

The influence of magnesium doping on the properties of tetrakis(thiourea)nickel(II) chloride crystals has been described. The reduction in the intensity observed in powder X-ray diffraction of doped specimen and slight shifts in vibrational frequencies confirm the lattice stress as a result of doping. Surface morphological changes due to doping of the alkaline earth metal are observed by scanning electron microscopy. The incorporation of Mg(II) into the crystal lattice was confirmed by energy dispersive X-ray spectroscopy. Lattice parameters are determined by single crystal XRD analysis. The thermogravimetric and differential thermal analysis studies reveal the purity of the materials and no decomposition is observed up to the melting point. The crystal is further characterized by Kurtz powder technique and dielectric studies.     

Structural effects on encapsulation as probed in redox-active core dendrimer isomers

Three pairs of isomeric, iron-sulfur core dendrimers were prepared. Each isomer pair was distinguished by a 3,5-aromatic substitution pattern (extended) versus 2,6-aromatic substitution pattern (backfolded). Several observations were made that supported the hypothesis that the iron-sulfur cluster cores were encapsulated more effectively in the backfolded isomers as compared to their extended isomeric counterparts. The backfolded isomers were more difficult to reduce electrochemically, consistent with encapsulation in a more hydrophobic microenvironment. Furthermore, heterogeneous electron-transfer rates for the backfolded molecules were attenuated compared to the extended molecules. From diffusion measurements obtained by pulsed field gradient spin-echo NMR and chronoamperometry, the backfolded dendrimers were found to be smaller than the extended dendrimers. Comparison of longitudinal proton relaxation (T(1)) values also indicated a smaller, more compact dendrimer conformation for the backfolded architectures. These findings indicated that the dendrimer size was not the major factor in determining electron-transfer rate attenuation. Instead, the effective electron-transfer distance, as determined by the relative core position and mobility in a dendrimer, is most relevant for encapsulation.