Benzo-fused Tri[8]annulenes as Molecular Models of Cubic Graphite

Cyclotrimerization of 9,10‐dibromo‐9,10‐dihydrodibenzo[3,4:7,8]cycloocta[1,2‐l]phenanthrene with potassium tert‐butoxide in the presence of a transition‐metal catalyst afforded two polycyclic aromatic hydrocarbon stereoisomers consisting of three cyclooctatetraene (COT) moieties connected via a central benzene ring. Both isomeric tri[8]annulenes were obtained selectively through the choice of the catalyst: The α,α,α‐form (Ru catalyst) displayed a threefold symmetrywith the COT subunits forming the side walls of a (chiral) molecular cup. In the thermodynamically more stable α,α,β‐isomer (Pd catalyst), one of the three boat‐shaped COTs was flipped over and faced the opposite molecular hemisphere with respect to the central benzene ring as evidenced by crystal structure analysis. Both title compounds are small segments of “cubic graphite”, an elusive carbon allotrope

Effects of Added Vegetation on Sand Bar Stability and Stream Hydrodynamics

Vegetation was added to a fully developed sandy point bar in the meander of a constructed stream. Significant changes in the flow structure and bed topography were observed. As expected, the addition of vegetative resistance decreased the depth-averaged streamwise velocity over the bar and increased it in the open region. In addition, the secondary circulation increased in strength but became confined to the deepest section of the channel. Over the point bar, the secondary flow was entirely outward, i.e., toward the outer bank. The changes in flow led to changes in bar shape. Although the region of the bar closest to the inner bank accumulated sediment, erosion of the bar and the removal of plants by scouring were observed at the interface between the planted bar and the open channel.National Science Foundation (U.S.) (Grant No. EAR 0738352

Gold-Catalyzed Stereoselective Domino Cyclization/Alkynylation of N-Propargylcarboxamides with Benziodoxole Reagents for the Synthesis of Alkynyloxazolines

A concise and highly stereoselective synthesis of alkynyloxazolines via a gold-catalyzed domino cyclization-alkynylation cascade of N-propargylcarboxamides with benziodoxole reagents is reported. This new protocol, which represents an attractive alternative to two step sequences based on Sonagashira couplings, offers a broad substrate scope, excellent functional group tolerance, and perfect stereoselectivity. A comparison of the computed energies of the isomers of the product suggests kinetic control as the cause of the observed selectivity

Bulky and Modular 3,3′-Bipyrazoles as Ligands: Synthesis, Characterization, and Catalytic Activity of Pd Complexes

In the present study, the properties of a new bidentate N,N′-chelating ligand class that bears an electron-excessive 3,3′-bipyrazole core have been investigated. The ligands are easily accessible in a three-step procedure by condensation with diethyl oxalate followed by tandem condensation with hydrazine hydrate and finally by aryl- or alkylation exclusively at the N-1,1′-pyrazole positions to furnish overall eleven new ligands with different electronic properties. After structural analysis of the ligands, their coordination to palladium, copper, and cobalt has been studied. These ligands coordinate the 2,2′-pyrazolyl nitrogen atoms in a bidentate fashion to the metals to realize complexes with an (L)MX2 motif. We present two crystal structures of Pd and Cu complexes, which to the best of our knowledge represent the first d8 and d9 2,2′-bipyrazole compounds coordinated through bidentate complexation. Initial catalytic experiments have been performed with palladium complexes with three bipyrazole ligands of this new class; the palladium-catalyzed copper-free Wacker oxidation of different alkenes showed superior activity compared to 2,2′-bipyridines. We attribute this to a higher redox potential of the 3,3′-bipyrazoles, which are ― besides electronic effects ― also strongly influenced by steric effects. These might be enforced by the extended ligand backbone, the choice of the wingtip substitution, and the smaller coordination cavity within the N2,N2′ atoms compared to 2,2′-bipyridine ligands

Homogeneous and heterogenised new gold C-scorpionate complexes as catalysts for cyclohexane oxidation

Gold(III) complexes of type [AuCl2{eta(2)-RC(R'pz)(3)}]Cl [R = R' = H (1), R = CH2OH, R' = H (2) and R = H, R' = 3,5-Me-2(3), pz = pyrazol-1-yl] were supported on carbon materials (activated carbon, carbon xerogel and carbon nanotubes) and used for the oxidation of cyclohexane to cyclohexanol and cyclohexanone, with aqueous H2O2, under mild conditions

Quinoidal Azaacenes: 99 % Diradical Character

Quinoidal azaacenes with almost pure diradical character (y=0.95 to y=0.99) were synthesized. All compounds exhibit paramagnetic behavior investigated by EPR and NMR spectroscopy, and SQUID measurements, revealing thermally populated triplet states with an extremely low-energy gap ΔEST′ of 0.58 to 1.0 kcal mol−1. The species are persistent in solution (half-life≈14–21 h) and in the solid state they are stable for weeks