Synthese und Struktur der basischen Erdalkalinitrate Sr2(OH)3NO3 und Ba2(OH)3NO3

Synthesis and Structure of the Basic Alkaline Earth Nitrates Sr₂(OH)₃NO₃ and Ba₂(OH)₃NO₃ Sr₂(OH)₃NO₃ and Ba₂(OH)₃NO₃ were synthesized from mixtures of freshly prepared strontium or barium hydroxides and their corresponding nitrates in evacuated quartz glass ampoules at 420 °C and 360 °C, respectively. Single crystals of Sr₂(OH)₃NO₃ were obtained in a solidified Sr(NO₃)₂ melt after subsequent heating and cooling cycles in air up to 600 °C. The crystal structure of the strontium compound was refined from single crystal and powder X‐ray data. Sr₂(OH)₃NO₃ crystallizes hexagonally in the space group (No. 189) with Z = 1 and the lattice parameters a = 6.624(2) Å and c = 3.560(1) Å (single crystal data). The powder pattern of Ba₂(OH)₃NO₃ was indexed isotypically to Sr₂(OH)₃NO₃ with the lattice parameters a = 6.9260(1) Å and c = 3.8086(1) Å, and the crystal structure was refined from powder X‐ray data. Alkaline earth ions in the structures are surrounded trigonal‐prismatically by six hydroxide ions. These prisms are sharing their trigonal faces along [001] building up columns. These columns are connected in the ab‐plane by shared edges, and form hexagonal tunnels with the nitrate groups stacked inside. Infrared and thermoanalytical data of Sr₂(OH)₃NO₃ are presented.     

Total synthesis of (-)-pseudolaric acid B

We report the enantioselective synthesis of pseudolaric acid B (1a), a diterpene acid isolated from the bark of Pseudolarix kaempferi Gordon, which displays interesting antifungal, antifertility, and cytotoxic activity against multidrug resistant cell lines. Our synthesis utilizes a highly efficient metal-catalyzed [5 + 2] vinylcyclopropane-alkyne intramolecular cycloaddition to construct the polyhydroazulene core of the natural product. Elaboration to the tricyclic scaffold of the pseudolaric acids was completed with an intramolecular alkoxycarbonyl radical cyclization to form the quaternary center and a highly diastereoselective cerium acetylide addition to a methyl ketone for introduction of the acid side chain.     

Low-temperature rapid-scan detection of reactive intermediates in epoxidation reactions catalyzed by a new enzyme mimic of cytochrome p450

The use of synthetic iron(III) porphyrins as models for heme-type catalysts in biomimetic cytochrome P450 research has provided valuable information on the nature and reactivity of intermediates produced in the "peroxide shunt" pathway. This article reports spectroscopic detection of reactive intermediates formed in the epoxidation reaction of cis-stilbene with m-chloroperoxybenzoic acid catalyzed by a new mimic of cytochrome P450 with a substituted RSO3- group (1). The application of low-temperature rapid-scan stopped-flow techniques enabled the determination of equilibrium and rate constants for the formation and decay of all intermediates in the catalytic cycle of 1, including the rate constant for the formation (1*+)FeIV=O and for oxygen transfer to the substrate. Noteworthy, the reaction of (1*+)FeIV=O with cis-stilbene leads to an almost complete re-formation (95%) of the starting complex 1. The results show that complex 1 is a valuable catalyst with promising properties for further applications in a biomimetic approach toward mimicking oxygenation reactions of cytochrome P450.     

Multimode Jahn-Teller and pseudo-Jahn-Teller interactions in the cyclopropane radical cation: complex vibronic spectra and nonradiative decay dynamics

The complex vibronic spectra and the nonradiative decay dynamics of the cyclopropane radical cation (CP+) are simulated theoretically with the aid of a time-dependent wave packet propagation approach using the multireference time-dependent Hartree scheme. The theoretical results are compared with the experimental photoelectron spectrum of cyclopropane. The ground and first excited electronic states of CP+ are of X2E' and A2E' type, respectively. Each of these degenerate electronic states undergoes Jahn-Teller (JT) splitting when the radical cation is distorted along the degenerate vibrational modes of e' symmetry. The JT split components of these two electronic states can also undergo pseudo-Jahn-Teller (PJT)-type crossings via the vibrational modes of e', a1' and a2' symmetries. These lead to the possibility of multiple multidimensional conical intersections and highly nonadiabatic nuclear motions in these coupled manifolds of electronic states. In a previous publication [J. Phys. Chem. A 2004, 108, 2256], we investigated the JT interactions alone in the X2E' ground electronic manifold of CP+. In the present work, the JT interactions in the A2E' electronic manifold are treated, and our previous work is extended by considering the coupling between the X2E' and A2E' electronic states of CP+. The nuclear dynamics in this coupled manifold of two JT split doubly degenerate electronic states is simulated by considering fourteen active and most relevant vibrational degrees of freedom. The vibronic level spectra and the ultrafast nonradiative decay of the excited cationic states are examined and are related to the highly complex entanglement of electronic and nuclear degrees of freedom in this prototypical molecular system.     

Vibrations and thermodynamics of clusters of polycyclic aromatic hydrocarbon molecules: the role of internal modes

The vibrational spectra of clusters of coronene molecules are theoretically calculated using a mixed quantum/classical scheme, each molecule being described by a tight-binding Hamiltonian, the intermolecular forces being provided by explicit Lennard-Jones and point charge sites. The normal modes of vibrations are shown to exhibit significant variations upon clustering. In particular, for large clusters intra- and intermolecular modes tend to mix and fill the mid-infrared range. We also calculate the heat capacity of the (C24H12)8 cluster as a function of temperature, emphasizing the isomerizations that take place during melting. Quantum delocalization effects, as obtained from the Pitzer-Gwinn semiclassical approximation, are important enough to wash out all signatures of the structural transitions on the caloric curve. On the basis of a simple two-state model we estimate that clusters containing about 300 molecules are required for melting to be detected on the caloric curve.     

Self-consistent field tight-binding model for neutral and (multi-) charged carbon clusters

A semiempirical model for carbon clusters modeling is presented, along with structural and dynamical applications. The model is a tight-binding scheme with additional one- and two-center distance-dependent electrostatic interactions treated self-consistently. This approach, which explicitly accounts for charge relaxation, allows us to treat neutral and (multi-) charged clusters not only at equilibrium but also in dissociative regions. The equilibrium properties, geometries, harmonic spectra, and relative stabilities of the stable isomers of neutral and singly charged clusters in the range n=1-14, for C(20) and C(60), are found to reproduce the results of ab initio calculations. The model is also shown to be successful in describing the stability and fragmentation energies of dictations in the range n=2-10 and allows the determination of their Coulomb barriers, as examplified for the smallest sizes (C(2) (2+),C(3) (2+),C(4) (2+)). We also present time-dependent mean-field and linear response optical spectra for the C(8) and C(60) clusters and discuss their relevance with respect to existing calculations.     

A generalization of an integral of Ramanujan

This paper considers a generalization of an integral introduced by S. Ramanujan in his third notebook. Ramanujan’s integral is itself a version of the dilogarithm,