Atom Exchange Versus Reconstruction: (GexAs4−x)x− (x=2, 3) as Building Blocks for the Supertetrahedral Zintl Cluster [Au6(Ge3As)(Ge2As2)3]3−

The Zintl anion (Ge₂As₂)^2? represents an isostructural and isoelectronic binary counterpart of yellow arsenic, yet without being studied with the same intensity so far. Upon introducing [(PPh₃)AuMe] into the 1,2‐diaminoethane (en) solution of (Ge₂As₂)^2?, the heterometallic cluster anion [Au₆(Ge₃As)(Ge₂As₂)₃]^3? is obtained as its salt [K(crypt‐222)]₃[Au₆(Ge₃As)(Ge₂As₂)₃]?en?2 tol ( 1 ). The anion represents a rare example of a superpolyhedral Zintl cluster, and it comprises the largest number of Au atoms relative to main group (semi)metal atoms in such clusters. The overall supertetrahedral structure is based on a (non‐bonding) octahedron of six Au atoms that is face‐capped by four (Ge_xAs_4?x)^x? (x=2, 3) units. The Au atoms bind to four main group atoms in a rectangular manner, and this way hold the four units together to form this unprecedented architecture. The presence of one (Ge₃As)^3? unit besides three (Ge₂As₂)^2? units as a consequence of an exchange reaction in solution was verified by detailed quantum chemical (DFT) calculations, which ruled out all other compositions besides [Au₆(Ge₃As)(Ge₂As₂)₃]^3?. Reactions of the heavier homologues (Tt₂Pn₂)^2? (Tt=Sn, Pb; Pn=Sb, Bi) did not yield clusters corresponding to that in 1 , but dimers of ternary nine‐vertex clusters, {[AuTt₅Pn₃]₂}^4? (in 2 – 4 ; Tt/Pn=Sn/Sb, Sn/Bi, Pb/Sb), since the underlying pseudo‐tetrahedral units comprising heavier atoms do not tend to undergo the said exchange reactions as readily as (Ge₂As₂)^2?, according to the DFT calculations.     

Asymmetric Hydroformylation Using a Rhodium Catalyst Encapsulated in a Chiral Capsule

Supramolecular capsules can be used to change the activity and selectivity of a catalyst through the influence of the second coordination sphere, reminiscent of how enzymes control the selectivity of their processes. In enzymes, this approach is used to also control the enantioselectivity of reactions in which the active catalytic site is often not chiral but the second coordination sphere is. We are interested in the possibility to generate a chiral second coordination sphere around an otherwise achiral transition metal complex for asymmetric catalysis. In this paper we show that the ligand template approach can be used to generate a chiral second coordination sphere around a rhodium complex, which is used in asymmetric hydroformylation.     

Synthesis of Structurally Complex Silicon Frameworks through the First Sila-Aldol Reaction

Herein, we report on the first sila-aldol reaction, which emphasizes the tight connection between silicon and carbon chemistry. This novel synthetic method provides straightforward access to 2-oxahexasilabicyclo[3.2.1]octan-8-ide, a structurally complex silicon framework, in quantitative yield. Its structure was confirmed by NMR spectroscopy and X-ray crystallography, and it displays a distinctive charge-transfer transition. The complete mechanism of this highly selective rearrangement cascade is outlined and supported by density functional theory (DFT) calculations, which highlight the thermodynamic driving force and the low activation barriers of this powerful silicon–carbon bond-forming strategy.     

Highly Stable,Low Gas Crossover,Proton-Conducting Phenylated Polyphenylenes

Two classes of novel sulfonated phenylated polyphenylene ionomers are investigated as polyaromatic-based proton exchange membranes. Both types of ionomer possess high ion exchange capacities yet are insoluble in water at elevated temperatures. They exhibit high proton conductivity under both fully hydrated conditions and reduced relative humidity, and are markedly resilient to free radical attack. Fuel cells constructed with membrane-electrode assemblies containing each ionomer membrane yield high in situ proton conductivity and peak power densities that are greater than obtained using Nafion reference membranes. In situ chemical stability accelerated stress tests reveal that this class of the polyaromatic membranes allow significantly lower gas crossover and lower rates of degradation than Nafion benchmark systems. These results point to a promising future for molecularly designed sulfonated phenylated polyphenylenes as proton-conducting media in electrochemical technologies.     

Quantification of Noncovalent Interactions in Azide–Pnictogen, –Chalcogen,and –Halogen Contacts

The noncovalent interactions between azides and oxygen-containing moieties are investigated through a computational study based on experimental findings. The targeted synthesis of organic compounds with close intramolecular azide–oxygen contacts yielded six new representatives, for which X-ray structures were determined. Two of those compounds were investigated with respect to their potential conformations in the gas phase and a possible significantly shorter azide–oxygen contact. Furthermore, a set of 44 high-quality, gas-phase computational model systems with intermolecular azide–pnictogen (N, P, As, Sb), –chalcogen (O, S, Se, Te), and –halogen (F, Cl, Br, I) contacts are compiled and investigated through semiempirical quantum mechanical methods, density functional approximations, and wave function theory. A local energy decomposition (LED) analysis is applied to study the nature of the noncovalent interaction. The special role of electrostatic and London dispersion interactions is discussed in detail. London dispersion is identified as a dominant factor of the azide–donor interaction with mean London dispersion energy-interaction energy ratios of 1.3. Electrostatic contributions enhance the azide–donor coordination motif. The association energies range from −1.00 to −5.5 kcal mol⁻¹.     

Important aspects in the formulation of solid–fluid debris-flow models. Part II. Constitutive modelling

This article points at some critical issues which are connected with the theoretical formulation of the thermodynamics of solid–fluid mixtures of frictional materials. It is our view that a complete thermodynamic exploitation of the second law of thermodynamics is necessary to obtain the proper parameterizations of the constitutive quantities in such theories. These issues are explained in detail in a recently published book by Schneider and Hutter (Solid–Fluid Mixtures of Frictional Materials in Geophysical and Geotechnical Context, 2009), which we wish to advertize with these notes. The model is a saturated mixture of an arbitrary number of solid and fluid constituents which may be compressible or density preserving, which exhibit visco-frictional (visco-hypoplastic) behavior, but are all subject to the same temperature. Mass exchange between the constituents may account for particle size separation and phase changes due to fragmentation and abrasion. Destabilization of a saturated soil mass from the pre- and the post-critical phases of a catastrophic motion from initiation to deposition is modeled by symmetric tensorial variables which are related to the rate independent parts of the constituent stress tensors.