High Stability of a Phosphenium Ion Allows Umpolung of P--H Bonds

The high intrinsic stability of 1,3,2-diazaphospholenium cations enhances ionic polarization of covalent P--X bonds in P -halogeno- and P -hydrido-diazaphospholenes. The physical properties of the latter suggest a hydridic nature of the P--H bond, and their reactivities display an "Umpolung" as compared to known reaction patterns of phosphines.     

Synthesis and Study of a Sulfur Heterocycle Fused p-Phenylene Vinylene Conducting Polymer

Abstract

Poly(benzo[1,2-b:4,5-b′]dithiophene-4,8-diyl vinylene) (1) has been prepared by the pyrolysis of the precursor polymer 2 and studied. Quantum mechanical calculations on the aromatic and quinoid monomers, oligomers and polymers indicate that 1 is a planar aromatic polymer.     

SOME REACTIONS OF 1,3-THIAZINE DERIVATIVES WITH ALIPHATIC DIAMINES

Abstract

A wide range of 2-substituted-5,6-dihydro-4H-1,3-thiazines (I) and tetrahydro-2H-1,3-thiazines (II) have been found to undergo a facile ring transformation reaction with aliphatic diamines to form the corresponding dinitrogen heterocycles (III) and (IV).     

Metal-Rich Phosphanediyl-and Arsanediyl-Clusters

Abstract

The reactions of primary silylphosphanes and -arsanes 1 with BuLi yield the three-dimensional M₂ER-aggregates 2 (E = P, As). We observed that the double lithiation of 1 in the presence of Li₂O results in the formation of the aggregates 3 and 4.     

Radical Copolymerization of Acrylic Monomers. II Effect of Solvent on Radical Copolymerization of Methyl Methacrylate and Styrene

The influence of various solvents on the copolymerization behavior of methyl methacrylate with styrene has been investigated. In these systems there is a significant solvent effect on both r_S and r_M which may be attributed to changes in the dielectric constant of the solvents used. The calculated relative reactivity of the polystyryl radical towards the methyl methacrylate monomer increases with increasing solvent polarity, whereas the reactivity of poly(methyl methacrylate) radical towards styrene monomer decreases. The results obtained are discussed taking into account the behavior of both monomers in homopolymerization with the same experimental conditions as in copolymerization.     

Radiation-Induced Copolymerization of Styrene and Cellulose at Low Dose Rates

A study has been made of the radiation-induced grafting of styrene to cellulose in the presence of cobalt 40 gamma irradiation at low total doses and dose rates. For copolymerization, What mans 41 filter paper was immersed in solutions of styrene in methanol at various monomer concentrations. The dose rates were varied from 140 to 3100 rads/hr while the total dose varied from lo³ to 2 × 10⁵ rads.

In the presence of oxygen the grafting results showed considerable scatter, but a statistical analysis revealed that at all concentrations a linear relationship existed between total dose and graft %. Three factors contributing to the variance about the regression line were examined. Residual oxygen in the solution, while not important at high dose rates, was shown markedly to contribute to the variance in the range examined. A linear dose-rate effect involving a decrease in graft with increasing dose rate was demonstrated. A LET effect also contributed to the over-all variance. Preliminary results indicate the presence of a maximum which may be a Trommsdorff effect.     

Synthesis and Complexation Studies of a Convex Bis-porphyrin Tweezer—A Molecular Capsule Precursor

The synthesis and spectroscopic studies of a convex bis-porphyrin based molecular tweezer are reported. The complexation of small bidentate ligands by metallated derivatives of the bis-porphyrin host were monitored through UV–visible and ¹H NMR spectroscopy and yielded large association constants.