“Organic Metals”—The Intermolecular Migration of Aromaticity

The electrical conductivity of a wide variety of organic materials is reviewed and a comparison made between those materials which transport charge efficiently and those that do not. This comparison reveals that the most efficient conductors contain molecules (a) whose radical ions form a new aromatic sextet upon one-electron oxidation or reduction and (b) whose aromaticity can migrate by mixed-valence interaction. The electrical data are presented in light of the chemistry of these materials and the importance of chemical bonding interactions in the electron transport process. Several new examples are discussed and directions for further research explored.     

“Charge transfer” polymerization—and the absence thereof!

Mechanisms for “charge‐transfer” spontaneous polymerizations and cycloadditions between electron‐rich olefins and electron‐poor olefins were reviewed. As for propagation, literature proposals involving charge‐transfer complexes were rejected. Instead, alternating copolymerization is ascribed to polar effects in free‐radical reactions. As for spontaneous initiation, literature proposals involving charge‐transfer complexes, with or without proton transfer, were rejected. Instead, the initiating species is postulated to be a tetramethylene zwitterion biradical, which may initiate either ionic homopolymerization or free‐radical copolymerization. A new hypothesis proposes that any interaction that brings vinyl monomers close together may facilitate tetramethylene formation and spontaneous polymerization. These interactions include Coulombic, acid–base, hydrophobic–hydrophilic and templating–tethering interactions. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2069–2077, 2001     

Determination of “solvent” concentration in “chromatographic solutions” on the cellulose sorbents

An attempt was undertaken to furnish an entirely quantitative characteristics to the thermodynamic model of the chromatographic system presented in (2). The attempt proved to be successful and one managed to establish simultaneously a new method enabling direct determination of the hydrogen-bond enthalpy from the PC experimental results.     

“Complex” versus “free radical” mechanism for the catalytic decomposition of H2O2 by ferric ions

Kinetic and spectrophotometric measurements made during the Fe³⁺ ion catalyzed decomposition of H₂O₂ have been analyzed using the computer simulation method. Improved values of the rate constants of the “complex scheme” and of the molar absorptivities ofthe intermediates were obtained: k₃/K_M = 4.94 M^?1 min^?1, k₄ = 193 M^?1 min^?1, ε_I/K_M = 52.3 M^?2 cm^?1, ε_II = 25.7 M^?1 cm^?1. The simulation revealed details of the reaction which were unavailable by other means and which explained several features of its kinetics. The total amount of O₂ evolved in the reaction using [H₂O₂] ～ 10^?2 M has been calculated and found to be nearly stoichiometric. O₂ evolution experiments in this region cannot, thus, distinguish between the “complex mechanism” predicting nearly stoichiometric evolution of O₂ and the “free radical mechanism” predicting exactly stoichiometricamounts of O₂. There are discrepancies within the “free radical scheme” with regard to the correct values of the rate constants to fit the reactions of H₂O₂ both with Fe²⁺ and Fe³⁺ ions, as well as other reactions assumed to proceed via free radicals.     

Discovery and Syntheses of “Superbug Challengers”—Platensimycin and Platencin

Bacteria have developed resistance to almost all existing antibiotics known today and this has been a major issue over the last few decades. The search for a new class of antibiotics with a new mode of action to fight these multiply‐drug‐resistant strains, or “superbugs”, allowed a team of scientists at Merck to discover two novel antibiotics, platensimycin and platencin using advanced screening strategies, as inhibitors of bacterial fatty acid biosynthesis, which is essential for the survival of bacteria. Though both these antibiotics are structurally related, they work by slightly different mechanisms and target different enzymes conserved in the bacterial fatty acid biosynthesis. This Focus Review summarizes the synthetic and biological aspects of these natural products and their analogues and congeners.     

The Correct Meaning of “Coating Efficiency” vs. the “Utilization of Theoretical Efficiency”

The correct meaning of the the term “utilization of the theoretical efficiency” vs. the “coating efficiency” is explained.     

[Fe(H2O)5(NO)]2+, the “Brown‐Ring” Chromophore

Although the “brown‐ring” ion, [Fe(H₂O)₅(NO)]²⁺ ( 1 ), has been a research target for more than a century, this poorly stable species had never been isolated. We now report on the synthesis of crystals of a salt of 1 which allowed us to tackle the unique bonding situation on an experimental basis. As a result of the bonding analysis, two stretched, spin‐polarised π‐interactions provide the Fe–NO binding—and challenge the concept of “oxidation state”.     

On the “Wolfsberg–Helmholz Conjecture” of “Extended‐Hückel Theory”

After having reviewed some pioneer integral approximations closely related to Rüdenberg's expansions of one‐ and two‐electron orbital products, we apply the previously described “Implicit Multi‐Center Integration” techniques on Roothaan's “restricted” Fock‐matrix components over standard atomic orbital bases. The resulting compact forms are very similar to the well‐known “Wolfsberg–Helmholz Conjecture” of “Extended‐Hückel Theory,” which relates the various off‐diagonal matrix elements of “restricted” Fock‐type to their corresponding diagonal counterparts. In this way, a “nonempirical Extended‐Hückel Theory” can be created. © 2012 Wiley Periodicals, Inc.     

The 1H and 13C nmr spectra of the “onium” salts of dithiacyclophanes

The ¹H and ¹³C nmr spectra of three cyclic sulphonium salts ol dithiacyclophanes have been recorded and compared with those of the open-chain analogue. The ¹H spectra indicate that methylation of the dithiacyclophanes gives a mixture of eonformational isorners with slightly different chemical shifts for the benzylic protons. The ¹³C spectra indicate that the smaller rings adopt an unsymmetrical conformation with respect to the aromatic ring but that in the larger ring studied, the aromatic carbon atoms are magnetically equivalent. The relevance of these results to the reactivity of the aromatic ring is discussed.     

Kinetics of the “a” and “b” band emissions of mercury excimers with added gases

The kinetics of the “a” and “b” band emissions arising from the ¹Σ ← ³O_u and ¹Σ ← ³l_u transitions of the diatomic mercury molecule at λ_max ～ 4850 Å and 3350 Å, respectively, have been studied at low concentrations of mercury in the presence of N₂, C₂H₆, C₃H₈, and N₂O. Rate constant values have been obtained for the following reactions of the excimer molecule: Hg₂(³l_u) + N₂ → Hg₂(³O_u) + N₂ and Hg₂(³O_u) + RH → Hg₂(¹Σ) + RH, where RH = C₂H₆ or C₃H₈. From a consideration of the detailed kinetics of band emissions, it was also possible to derive rate constants for the quenching reactions of Hg(³P₀) atoms. These values are in reasonable agreement with those obtained previously from monitoring atom concentrations directly by 4047 Å absorbiometry.     

The preparation,structure and reactions of some “malonyl-α-aminopyridines”

The reaction of several substituted 2-aminopyridines with diethyl malonate was studied. The “methylmalonyl-α-aminopyridines” were shown to exist in the same tautomeric form as “malonyl-α-aminopyridine”. Formylation of these compounds takes place in the 3-position and has led to the formation of a new tricyclic compound.