Mono- and dinuclear molybdenum complexes with sterically demanding cycloheptatrienyl ligands

Sterically demanding cycloheptatrienylium (tropylium) salts of the type (1,3,5-C7H4R3)BF4 [R = t-Bu, (3a)BF4; R = SiMe3, (3b)BF4] have been prepared from the corresponding 1,3,5-trisubstituted benzene derivatives 1 by ring expansion with diazomethane followed by hydride abstraction with triphenylcarbenium tetrafluoroborate, (Ph3C)BF4. Complexation can be achieved by arene exchange and Mo(CO)3 group transfer employing [(eta6-p-xylene)Mo(CO)3] (4) to yield the cationic complexes (5)BF4. In refluxing mesitylene, [(eta7-C7H4t-Bu3)Mo(CO)3]BF4, (5a)BF4, undergoes CO substitution to furnish the mesitylene sandwich complex (6a)BF4. A cyclic voltammetric study reveals that this complex exhibits a reversible one-electron oxidation to the dicationic 17e complex 6a2+, which can also be accessed by chemical oxidation with AgBF4. On the contrary, the reduction of 6a+ is irreversible and does not yield a stable 19e complex 6a. To study the fate of the reduced 19e form, (5a)BF4 was treated with Na2Hg to diastereoselectively afford the C-C coupled bicycloheptatriene complex 7a. Paramagnetic, dinuclear complexes of the type [(eta7-C7H4R3)Mo(mu-Cl)3Mo(eta7-C7H4R3)] (8) have been obtained from the reaction of (5)BF4 with Me3SiCl. These can be regarded as mixed-valence Mo(0)/Mo(+I) compounds with a metal-metal bond order of 0.5. Cyclic voltammetric studies reveal that both complexes 8a and 8b undergo reversible one-electron oxidation as well as reduction. Treatment with one equivalent of ferrocenium hexafluorophosphate leads to removal of the unpaired electron and formation of the diamagnetic complexes (8)PF6. Theoretical DFT calculations have been carried out to further elucidate the bonding in these systems. In addition, the X-ray crystal structures of (5b)BF4, (6a)BF4 x CH2Cl2, (6a)(BF4)2 x (acetone)2, 7a x CH2Cl2, 8a x 0.5C6H14, and (8a)PF6 x Et2O are reported.     

Structural information content of networks: graph entropy based on local vertex functionals

In this paper we define the structural information content of graphs as their corresponding graph entropy. This definition is based on local vertex functionals obtained by calculating j-spheres via the algorithm of Dijkstra. We prove that the graph entropy and, hence, the local vertex functionals can be computed with polynomial time complexity enabling the application of our measure for large graphs. In this paper we present numerical results for the graph entropy of chemical graphs and discuss resulting properties.     

Formation of a mesoscopic skin barrier in mesoglobules of thermoresponsive polymers

With the combination of molecular scale information from electron paramagnetic resonance (EPR) spectroscopy and meso-/macroscopic information from various other characterization techniques, the formation of mesoglobules of thermoresponsive dendronized polymers is explained. Apparent differences in the EPR spectra in dependence of the heating rate, the chemical nature of the dendritic substructure of the polymer, and the concentration are interpreted to be caused by the formation of a dense polymeric layer at the periphery of the mesoglobule. This skin barrier is formed in a narrow temperature range of ~4 K above T(C) and prohibits the release of molecules that are incorporated in the polymer aggregate. In large mesoglobules, formed at low heating rates and at high polymer concentrations, a considerable amount of water is entrapped that microphase-separates from the collapsed polymer chains at high temperatures. This results in the aggregates possessing an aqueous core and a corona consisting of collapsed polymer chains. A fast heating rate, a low polymer concentration, and hydrophobic subunits in the dendritic polymer side chains make the entrapment of water less favorable and lead to a higher degree of vitrification. This may bear consequences for the design and use of thermoresponsive polymeric systems in the fast growing field of drug delivery.     

New Silver Tellurates – The Crystal Structures of a Third Modification of Ag2Te2O6 and of Ag4TeO5

Single crystals of a third modification of Ag₂Te₂O₆ (denoted as Ag₂Te₂O₆–III) and of Ag₄TeO₅ have been obtained as minor by‐products during hydrothermal phase formation experiments in the system Ag‐Hg‐Te‐O. The crystal structure of Ag₂Te₂O₆–III (P2₁/c, Z = 4, a = 6.4255(10), b = 6.9852(11), c = 13.204(2) Å, β = 90.090(3)°, 1885 independent reflections, R[F² > 2σ(F²)] = 0.0334, wR2(F² all) = 0.0817) comprises tellurium in oxidation states +IV and +VI and is topologically related to the structure of the Ag₂Te₂O₆–I modification, which consists of similar layers and interjacent layers of Ag⁺ cations. Ag₄TeO₅ (C2/c, Z = 8, a = 16.271(2), b = 6.0874(10), c = 11.4373(16) Å, β = 106.730(10)°, 2372 independent reflections, R[F² > 2σ(F²)] = 0.0288, wR2(F² all) = 0.0737) is made up of a layer‐like arrangement of isolated [Te^VI₂O₁₀] double octahedra and of Ag⁺ cations situated both in layers parallel and inside the layers of the anionic moieties.     

Weak itinerant magnetism as inhibited superconductivity

Thep-state pairing idea proposed recently to explain the ferromagnetism of ZrZn₂ is described in more detail, and the underlying soft-mode hypothesis is examined in relation with experiments, in particular the discovery of antiferromagnetism in TiBe₂. The key result, namely an electron-phonon contribution to the Stoner factor given essentially by the mass enhancement factor, is used to explain the behaviour of the Curie pointT _m and to predict an isotope effect.p-state superconductivity with a transition temperature determined by is predicted in TiBe₂ and, above the critical pressure whereT _m =0, also in ZrZn₂.Work in La Jolla supported by NSF/DMR 77-08469.     

A model of the chemical bond must be rooted in quantum mechanics, provide insight, and possess predictive power

In this response to the preceding paper by Bader, we show that the core arguments and statements presented in the latter are flawed. We argue that it is insufficient for a model of the chemical bond to be rooted in quantum mechanics. A good model must in addition provide insight and possess predictive power. Our molecular orbital (MO) model of the chemical bond, in particular, the associated energy-decomposition approach satisfies all these conditions. On the other hand, Atoms-in-Molecules (AIM) theory is only rooted in quantum mechanics as far as its mathematical framework is concerned. The physical status of its central concepts is not so clear. In particular, "bond paths" and "bond critical points" are once more confirmed not to be indicators of a stabilizing interaction. Moreover, AIM theory lacks any predictive power. We also address specific questions raised in the preceding paper. Finally, interpreting chemical bonding implies choosing a perspective on this phenomenon. That there are many perspectives is a matter of fact and this is in no way unphysical. What is unscientific is to claim uniqueness and truth for one of these choices, namely AIM, and to dismiss on this ground all other approaches.     

Calixarenes as hosts for ammonium cations: a quantum chemical study and mass-spectrometric investigations

Host-guest complexes of tetramethylcavitand with different ammonium cations were investigated by using a quantum chemical method at the density functional level (BP86, B3 LYP). The NH4+ cation is strongly bound to the host. Increasing methyl substitution at the cation decreases its inclination towards the complex formation. The calculated data are in line with results from electrospray ionization mass spectrometry (ESI-MS) experiments. They reveal stable aggregates only for the NH4+ cation and for the primary alkylammonium cations.     

Incorporation of carbon originating from CO2 into different compounds of soil microbial biomass and soil organic matter

In general, soils without the vegetation growing on them are regarded as sources of CO2. However, there are indications that CO2 is also fixed by soil microorganisms. Although this process is not significant from a quantitative point of view, it may change the isotopic composition of soil organic matter. Therefore, we conducted an incubation study with soil and 13C-labeled CO2 to investigate this process. We found that the label was transferred from CO2 into organic compounds in soil. At the end of a 61-day incubation period, 1.3 micromol C g(-1) soil, corresponding to approximately 0.08% of the soil organic carbon, had been fixed. CO2 may, therefore, be an additional source of soil organic carbon. Compound-specific analysis of amino sugars, amino acids, and fatty acids indicated that the label is incorporated into microbial, mainly bacterial, biomass. All groups of microorganisms were involved in the assimilation of CO2, but the relatively high enrichment of mono-unsaturated and mid-chain branched fatty acids indicates that gram negative bacteria and actinomycetes may be slightly more important in this process than other groups of microorganisms.     

Systematic optimisation of high-performance liquid chromatographic separation by varying the temperature, gradient, and stationary phase

Optimisation of the separation of a synthetic drug mixture by HPLC is performed by changing both continuous variables, i.e. mobile phase composition and temperature, and categorical variables, here the stationary phase. The retention of solutes is described on the basis of a general linear model in which the different columns are modelled by indicator variables. From the solute-specific retention models the global separation optimum is evaluated on the basis of multidimensional window diagrams using relative retentions of all peak pairs as the figure-of-merit.     

Electrochemical characterization of screen-printed carbonaceous electrodes for the determination of peroxidase activity in novel screen-printed flow-through modules

A novel totally screen-printed flow-through cell for immunoanalysis is presented. It contained screen-printed carbonaceous electrodes, which allowed the determination of peroxidase activity through the electrochemical reduction of p-benzoquinone. As different electrode materials differ strongly in their electrochemical properties, electrodes resulting from various screen-printable carbonaceous pastes were characterized using the hydroquinone/ p-benzoquinone redox couple. For most of the electrodes, cyclic voltammogram peak separations of between 550 and 670 mV were observed indicating only quasi-reversible electrochemical behavior. This was confirmed by variation of the peak separation with scan rate. Heterogeneous electron transfer rates of ca. 0.5 - 1 x 10(-3) cm s(-1) and electrochemical activation energies of ca. 20 kJ mol(-1) were found. These flow-through cells were not only applied to electrochemical peroxidase activity determinations but also, in combination with a separate detector, as affinity reactors. After biotinylation of screen-printed layers, streptavidin and then biotinylated peroxidase could be bound. However, as signals were only 10-20% of those obtained with a column filled with biotinylated glass beads, only the screen-printed electrochemical detector was applied to the detection of antibodies against the African Swine Fever Virus.