Pentadienyls vs cyclopentadienyls and reversal of metal-ligand bonding affinity with metal oxidation state: synthesis, molecular structures, and electronic structures of high-valent zirconium pentadienyl complexes

Molecules of the form Cp(6,6-dmch)ZrX(2) (Cp = eta(5)-cyclopentadienyl, X = Cl, Br, I; 6,6-dmch = eta(5)-6,6-dimethylcyclohexadienyl) have been synthesized, and the molecular and electronic structures have been investigated. These molecules allow direct comparison of the bonding and properties of pentadienyl and cyclopentadienyl ligands in the same high-oxidation-state metal complexes. Unlike the well-known Cp(2)ZrX(2) analogues, these Cp(6,6-dmch)ZrX(2) molecules are intensely colored, indicating significantly different relative energies of the frontier orbitals. Also unusual, the average Zr-C distances to the 6,6-dmch pentadienyl ligand are about 0.1 A longer than the average Zr-C distances to the cyclopentadienyl ligand for these Zr(IV) complexes, opposite of what is observed for the Zr(II) complex Cp(2,6,6-tmch)Zr(PMe(3))(2) (tmch = eta(5)-2,6,6-trimethylcyclohexadienyl), reflecting a dramatic reversal in the favorability of the bonding depending on the metal oxidation state. The experimental and computational results indicate that the color of the Cp(6,6-dmch)ZrX(2) complexes is due to a 6,6-dmch ligand-to-metal charge-transfer band. Compared to the Cp(2)ZrX(2) analogues, the Cp(6,6-dmch)ZrX(2) molecules have a considerably less stable HOMO that is pentadienyl-based and an essentially unchanged metal-based LUMO. Also, the lowest unoccupied orbital of pentadienyl is stabilized relative to cyclopentadienyl and becomes a better potential delta electron acceptor, thus contributing to the differences in structure and reactivity of the low-valent and high-valent metal complexes.     

pH sensitivity of Si--C linked organic monolayers on crystalline silicon surfaces.

The electrochemical behavior of Si--C linked organic monolayers is studied in electrolyte-insulator-Si devices, under conditions normally encountered in potentiometric biosensors, to gain fundamental knowledge on the behavior of such Si electrodes under practical conditions. This is done via titration experiments, Mott-Schottky data analysis, and data fitting using a site-binding model. The results are compared with those of native SiO(2) layers and native SiO(2) layers modified with hexamethyldisilazane. All samples display pH sensitivity. The number of Si--OH groups on the alkylated samples is calculated to be less than 0.7 % of that of a pure SiO(2) insulator, which still causes a pH sensitivity of approximately 25 mV per pH unit in the pH range: 4-7. The alkylated samples hardly suffer from response changes during up- and down-going titrations, which indicates that very little oxide is additionally formed during the measurements. The pK(a) values of all samples with monolayers (4.0-4.4) are lower than that of native SiO(2) (6.0). The long-term drift (of approximately 1 mV h(-1)) is moderate. The results indicate that biosensors composed of alkylated Si substrates are feasible if a cross-sensitivity towards pH in the sensor signal is taken into account.     

Phase Equilibria and Critical Curves of Binary Ammonia–Hydrocarbon Mixtures

Liquid or dense supercritical ammonia has been suggested as an extraction fluid. It is indeed good solvent for very different classes of compounds, as can be seen from phase diagrams. Such diagrams for binary systems of ammonia and hydrocarbons are presented and discussed on the basis of their critical curves. Apparatus and methods for the measurement of phase equilibria and equation of state data of fluid mixtures at high pressure are described.     

Algebraic spatial correlations in lattice gas automata violating detailed balance

In this paper we discuss the existence of generic long-range correlations in spatially homogeneous and stable equilibrium states of closed lattice gas automata whose stochastic collision rules violate the symmetry conditions of detailed balance and in addition satisfy local conservation laws. Such correlations occur even though the collision rules are strictly local and invariant under all symmetries of the lattice. First a phenomenological (Langevin equation) approach is discussed. Next we present a theoretical analysis on the basis of an approximate microscopic (ring kinetic) theory. This theory is used to calculate the amplitude ofr ^– tails in the spatial correlations, and the result is compared with computer simulations.     

Spectroscopy of alkali atoms and molecules attached to liquid He clusters

Large helium clusters, ranging in size from a few hundred to several thousand atoms, are produced in a nozzle expansion. Combining this source with a pick-up scattering cell in which the clusters can be seeded with chromophores allows us to probe the influence of the helium environment on the atoms and molecules attached to the clusters. Using an alkali as chromophore we recorded laser induced fluorescence spectra of Na atoms and molecules attached to helium clusters. Apart from the spectrum of the Na monomer, we have found spectroscopic bands which can unambiguous be assigned to two bound Na atoms. The first of this bands is due to 1^{1 +} (A) 1¹ _g ⁺ (X) excitations of the covalently bound singlet Na₂ molecule while the second is due to 1³ _g ⁺ 1^{3 +} excitations for the van der Waals bound triplet Na₂ dimer. Both bands have been vibrationally resolved. Furthermore we found very large fluorescence intensities in the region 605–635 nm which are likely due to the excitation of a species containing three Na atoms attached to a helium cluster.