Equilibria in complexes of N-heterocyclic molecules,part XII. The reaction of hydroxide and alkoxide Ions with platinum(II) complexes of 5-nitro-1,10-phenanthroline and 2,2′-bipyridyl

Summary Bis-(5-nitro-1,10-phenanthroline)platinum(II) dichloride and diperchlorate have been prepared. The reaction between the parent cation and hydroxide ion has been studied using 1 FI n.m.r. spectroscopy and found to involve attack at the ligand. The bis-(2,2-bipyridyl)platinum(II) ion has been shown to be highly reactive towards methoxide ion. The dissociation of a 2,2-bipyridyl ligand is preceded by attack at the ligand.Part XI: R. D. Gillard, t.. A. P. Kane-Maguire and P. A. Williams,Transition Met. Chem., 2, 47 (1977).On leave from the University of Baghdad, Iraq.     

Alkyl–oxygen bond formation in the mass spectra of α-chloromethyl aryl sulphones

When subjected to electron-impact, chloromethyl aryl sulphones (II, X = Cl) fragment predominantly by the loss of CH₂Cl from the molecular ion followed by the loss of SO₂ and in most cases the appropriate metastable peaks are present to confirm the transitions. In addition, alkyl–oxygen bond formation in the molecular ion was revealed by the presence of prominent peaks corresponding to the [R? ?-SO]⁺ ions. In most spectra no evidence for aryl–oxygen bond formation could be found and thus the presence of the chlorine atom was able to effectively reverse the direction of skeletal rearrangement reported for aryl methyl sulphones.     

Palladium-induced cyclizations for the synthesis of cis-2,5-disubstituted-3-methylenetetrahydrofurans: studies of the C7-C22 core of amphidinolide K

[formula: see text] The diastereoselective synthesis of cis-2,5-disubstituted-3-methylenetetrahydrofurans via Pd(0)-catalyzed cyclization of 2-methylene-1,4-diols is described. Investigations into the scope of the reaction and its application toward the synthesis of amphidinolide K is reported.     

A concise asymmetric synthesis of the ADE fragment of nakadomarin A

The ADE fragment of nakadomarin A has been synthesized in nine linear steps from commercial material. The key transformation is an asymmetric azomethine ylide [1,3]-dipolar cycloaddition to establish the AD-spirocyclic system containing three of the four stereocenters of the natural product. [reaction: see text]     

Homolytic reactions of polyfluoroaromatic compounds V. The reaction of pentafluorophenyl radicals with fluorobenzene

The arylation of fluorobenzene with pentafluorophenyl radicals obtained by the reaction of the corresponding aniline with pentyl nitrite is described. The reaction involves attact at the 2t?-,3t?-and 4t?-positions. The composition of the mixture and the nature of its components were determined by ¹⁹F NMR spectroscopy and were confirmed by gas-liquid chromatography.     

Application of Molecular Weight and Particle Growth Measurements in Continuously Uniform Latices to Kinetic Studies of Styrene Emulsion Polymerization

It is possible to generate, in specially formulated styrene emulsion polymerizations, latices in which the monomer—polymer particles are uniform through all stages of growth. These latices are kinetically similar to their polydispersed counterparts and can therefore be used as model systems in generalized kinetic studies of emulsion polymerization. The most important feature of these systems is the fact that the particles are uniform throughout the reaction with regard to all intrinsic properties and rate processes, and the particles can be characterized by this complete, continuous uniformity. Certain remarkably simple, but precise, relationships exist between the overall, measurable kinetic parameters and the individual particle kinetic parameters, thereby resulting in a heretofore unrealized analytic accessibility. Molecular weight kinetic analyses are an order of magnitude more accurate than in non-uniform systems. Application of these continuously uniform systems in actual kinetic studies indicates an inconsistency in the current concepts of emulsion polymerization, i.e., the generation of polymer at a constant molecular weight is predicted while an increase of several fold is observed. Before the situation can be clarified, further studies with continuously uniform systems are needed to evaluate molecular weight development, molecular weight distribution, and molecular structure and also to re-evaluate the rate and diffusion processes which control these structural features.     

Measurement/data-processing method to improve the ruggedness of membrane-based sensors: Application to amperometric oxygen sensor

This paper describes alternative measurement and data-processing approaches that can reduce effects of experimental variables on results obtained with a membrane-based sensor for oxygen. In the new approaches, the membrane-based sensor is first equilibrated with the sample solution, after which a polarizing voltage is applied and current vs. time data are recorded as the response decays toward a steady-state condition. Current vs. time data are then processed by a fixed-time option and an integration option designed to determine the charge corresponding to the total amount of oxygen inside the membrane when a polarizing voltage is applied. The current measured at a fixed time and the total charge varied linearly with oxygen concentration between 0.05 and 0.26 mmol l(-1). Pooled relative standard deviations (N = 35) for the measurement/data-processing step were near 0.4% for the new pre-equilibrium options compared to a value of 0.3% for the steady-state option. Dependencies of the pre-equilibrium options on membrane thickness and stirring rate in the most sensitive regions were at least two orders of magnitude smaller than for the steady-state option.