Time-displaced correlation functions in an infinite one-dimensional mixture of hard rods with different diameters

Time-displaced conditional distribution functions are calculated for an infinite, one-dimensional mixture of equal-mass hard rods of different diameters. The kinetic equation that describes the time dependence of the one-particle total distribution function is found to be non-Markovian, in contrast with the situation in systems of identical rods. The correlation function does not contain any isolated damped oscillation, except for systems of equal-diameter rods with discrete velocities. Thus, we generalize the one-component results of Lebowitz, Perçus, and Sykes, removing some nontypical features of that system.Supported by NSF grant No. MCS 75-21684 A01 (M. A.), NSF grant No. MPS 75-20638 (J. L.), and USAFOSR grant No. 73-2430 B (J. M.)John Guggenheim Fellow on sabbatical leave from Belfer Graduate School of Science, Yeshiva University, New York.     

Stereospecific synthesis of N-(1-phenylethyl)-2,4,5-triphenyloxazolidines

Treatment of the diastereoisomeric N-(1-phenylethyl)-1,2-diphenyl-2-aminoethanols with benzaldehyde yields stereospecifically N-(1-phenylethyl)-2,4,5-triphenyloxazolidines with four chiral centers. The configurations of these oxazolidines are established through their ring-opening reactions with methylmagnesium iodide and subsequent oxidation with lead tetracetate.     

New Dienophiles: 1-Acetylvinyl Arenecarboxylates. Reactivity toward cyclopentadiene and exocyclic dienes

The preparations of 1-acetylvinyl arenecarboxylates H₂C=C(COCH₃)OCOR with R = phenyl, p-nitrophenyl, 2,4-dinitrophenyl, α- and β-naphthyl are described (3) . The Diels-Alder reactivity of these dienophiles toward cyclopentadiene is evaluated and compared with that of methyl vinylketone, 3-trimethylsilyloxy-, 3-ethoxy- and 3-acetoxy-3-buten-2-ones. The stereoselectivity of the cycloadditions of these dienophiles with 2,3,5,6-tetramethylidene-7-oxanorbornane (1) and 5,8-dimethoxy-1,4-epoxy-2,3-dimethylidene-1,2,3,4-tetrahydroanthracene (2) is studied. In principle, the dienophiles 3 allow direct functionalization of the position C(9) of the A-ring of daunomycinone analogs by Diels-Alder additions to exocyclic dienes such as 1 and 2 .     

Electron pairing and chemical bonds. Electron fluctuation and pair localization in ELF domains

This article reports the numerical comparison of the quantities characterizing the extent of electron fluctuation and pair localization in the domains determined by the direct minimization of electron fluctuation with the domains resulting from the partitioning of the molecules based on the topological analysis of the so-called electron localization function (ELF). Such a comparison demonstrates that the ELF partitioning can be regarded as a feasible alternative to computationally much more demanding direct optimization of minimum fluctuation domains. This opened the possibility of the systematic scrutiny of the electron pair model of the chemical bond, and as it was demonstrated, the previous pessimistic claims about the applicability of this model are not completely justified.     

On computationally adjusting the Hill equation of adsorption

We discuss the implementation and computational efficiency of one approach to adjusting the Hill equation of adsorption to a set of empirical data, pointing out some aspects that seem to be valid in the general case. The approach consists basically of minimizing squares of deviations of the adsorbed amounts, which are numerically computed in terms of the empirical pressures and the parameters. Hill's equation is dealt with as a prototype of nonlinear equations seldom used by chemists because none of their variables can be set free.     

(Benzimidazol-1-yl)methyl]benzamides as bifunctional reagents for reliable inorganic-organic supramolecular synthesis

A series of ligands that utilize five-membered N-heterocycles as coordination sites, and the self-complementarity of the carboxamide functionality, have been employed in the supramolecular synthesis of Ag(I)-based extended networks. The crystal structures of eight compounds are reported: bis[4-(2-methylbenzimidazol-1-yl)methylbenzamide]silver(I) tetrafluoroborate hydrate methanol, 1; bis[3-(2-methylbenzimidazol-1-yl)methylbenzamide]silver(I) tetrafluoroborate, 2; bis[4-(5,6-dimethylbenzimidazol-1-yl)methylbenzamide]silver(I) tetrafluoroborate, 3; bis[4-(2-methylbenzimidazol-1-yl)methylbenzamide]silver(I) hexafluoroarsenate methanol, 4; bis[3-(2-methylbenzimidazol-1-yl)methylbenzamide]silver(I) hexafluoroarsenate methanol(0.5), 5; bis[4-(5,6-dimethylbenzimidazol-1-yl) methylbenzamide]silver(I) hexafluoroarsenate, 6; bis[4-(2-methylbenzimidazol-1-yl)methylbenzamide]silver(I) hexafluoroantimonate, 7; and bis[3-(2-methylbenzimidazol-1-yl)methylbenzamide]silver(I) hexafluoroantimonate, 8. An analysis of motifs and structural patterns that result from the primary intermolecular interactions in these structures, reveals that this family of ligands is capable of providing quite reliable means for propagating the linear geometry of the complex ions into extended 1-D architectures via ligand-ligand, N-H...O, hydrogen-bond interactions.     

Effect of Pd nanoparticle size on the catalytic hydrogenation of allyl alcohol

We report a particle size dependence for the rate of hydrogenation of allyl alcohol using 1.3-1.9 nm Pd dendrimer-encapsulated nanoparticle (DEN) catalysts. For particles with diameters of <1.5 nm and containing <147 Pd atoms, the modulation in catalytic activity is due to the electronic properties of the particle. For the larger particles, 1.5-1.9 nm in diameter and containing an average of 147-250 Pd atoms, the size effect is a result of geometrical constraints. Specifically, the hydrogenation reaction is shown to occur preferentially on the face atoms of the larger nanoparticles.     

Regioselective electrophilic additions to 2-alkoxy- and 2-alkoxymethyl-7-oxabicyclo [2.2.1] hept-5-ene derivatives

The influence of the stereochemistry at C-2 on the selectivity of the reaction between PhSeBr and 2-alkoxymethyl substituted oxanorbornenes has been studied. All endo isomers displayed complete regio- and stereocontrol with incorporation of the electrophile on C-5.