Copper Complexes with Diazoolefin Ligands and their Photochemical Conversion into Alkenylidene Complexes

Homometallic copper complexes with alkenylidene ligands are discussed as intermediates in catalysis but the isolation of such complexes has remained elusive. Herein, we report the structural characterization of copper complexes with bridging and terminal alkenylidene ligands. The compounds were obtained by irradiation of Cu^I complexes with N-heterocyclic diazoolefin ligands. The complex with a terminal alkenylidene ligand required isolation in a crystalline matrix, and its structural characterization was enabled by in crystallo photolysis at low temperature.     

A numerical investigation of transient detonation in granulated material

A two-phase model based upon principles of continuum mixture theory is numerically solved to predict the evolution of detonation in a granulated reactive material. Shock to detonation transition (SDT) is considered whereby combustion is initiated due to compression of the material by a moving piston. In particular, this study demonstrates the existence of a SDT event which gives rise to a steady two-phase Chapman-Jouguet (CJ) detonation structure consisting of a single lead shock in the gas and an unshocked solid; this structure has previously been independently predicted by a steady-state theory. The unsteady model equations, which constitute a non-strictly hyperbolic system, are numerically solved using a modern high-resolution method. The numerical method is based on Godunov's method, and utilizes an approximate solution for the two-phase Riemann problem. Comparisons are made between numerical predictions and known theoretical results for 1) an inert two-phase shock tube problem, 2) an inert compaction wave structure, and 3) a reactive two-phase detonation structure; in all cases, good agreement exists. Received 4 August 1995 / Accepted 17 February 1996     

Isolation and Crystallographic Characterization of Two,Nonisolated Pentagon Endohedral Fullerenes: Ho3N@C2(22010)-C78 and Tb3N@C2(22010)-C78

Purified samples of Ho₃N@C₂(22010)-C₇₈ and Tb₃N@C₂(22010)-C₇₈ have been isolated by two distinct processes from the rich array of fullerenes and endohedral fullerenes present in carbon soot from graphite rods doped with Ho₂O₃ or Tb₄O₇. Crystallographic analysis of the endohedral fullerenes as cocrystals with Ni(OEP) (in which OEP is the dianion of octaethylporphyrin) shows that both molecules contain the chiral C₂(22010)-C₇₈ cage. This cage does not obey the isolated pentagon rule (IPR) but has two sites where two pentagons share a common C−C bond. These pentalene units bind two of the metal ions, whereas the third metal resides near a hexagon of the cage. Inside the cages, the Ho₃N or Tb₃N unit is planar. Ho₃N@C₂(22010)-C₇₈ and Tb₃N@C₂(22010)-C₇₈ use the same cage previously found for Gd₃N@C₂(22010)-C₇₈ rather than the IPR-obeying cage found in Sc₃N@D_3h-C₇₈.     

Exploiting the Potential of Meroterpenoid Cyclases to Expand the Chemical Space of Fungal Meroterpenoids

Fungal meroterpenoids are a diverse group of hybrid natural products with impressive structural complexity and high potential as drug candidates. In this work, we evaluate the promiscuity of the early structure diversity-generating step in fungal meroterpenoid biosynthetic pathways: the multibond-forming polyene cyclizations catalyzed by the yet poorly understood family of fungal meroterpenoid cyclases. In total, 12 unnatural meroterpenoids were accessed chemoenzymatically using synthetic substrates. Their complex structures were determined by 2D NMR studies as well as crystalline-sponge-based X-ray diffraction analyses. The results obtained revealed a high degree of enzyme promiscuity and experimental results which together with quantum chemical calculations provided a deeper insight into the catalytic activity of this new family of non-canonical, terpene cyclases. The knowledge obtained paves the way to design and engineer artificial pathways towards second generation meroterpenoids with valuable bioactivities based on combinatorial biosynthetic strategies.     

Wavelength tunable high power laser using a double-clad Er:Yb doped fiber

We experimentally demonstrated a stable, wavelength-tunable fiber laser using a polarization-maintaining, double-clad Er:Yb doped fiber amplifier in the cavity. The output wavelength is tunable over the range from 1535 to 1567 nm using a fixed grating and the dichroic mirror placed on a rotational mount; under rotation of the dichroic mirror the tuning ratio of 50 nm/deg was found. We studied the wavelength tuning range dependence on the amplifier fiber length and achieved a maximal output power of 850 mW. This configuration can be Q-switched for high peak power and its narrow bandwidth is suitable for nonlinear optics applications, such as parametric teraherthz generator.     

The influence of substrate surface roughness on microstrip transmission line loss using conventional analyses and length‐scale fractal analysis

Two components of conductor topography can impact conductor loss for signals in the GHz frequency range: conductor–ceramic interface roughness and conductor edge angle. This study is an experimental investigation of the influence of these conductor topographies on conductor loss in microstrip circuits produced by thick‐film technology. The aluminum nitride ceramic substrates have different surface roughnesses due to different surface finish processes. The substrate surfaces were characterized using conventional and length‐scale fractal analysis. The conductor–ceramic interface was measured with a contact profilometer. The conductor edge angle and conductor edge profile were measured optically. It was found that there is a direct correlation between conductor loss and conductor edge angle, whereas there is an inverse correlation between loss and substrate roughness or relative length of the conductor–ceramic interface. This is the opposite result to the conventional expectation of surface roughness effects on conductor loss. There is also a negative correlation between conductor edge angle and surface roughness or relative length. The loss behavior can be explained by the interaction of the conductor paste with the surfaces during processing. The paste tends to spread more on the smoother surfaces, and thus creates an elongated edge of diminishing cross‐section and a small edge angle. This leads to greater conductor loss. Copyright © 2009 John Wiley & Sons, Ltd.     

C−H Activation of Inert Arenes using a Photochemically Activated Guanidinato-Magnesium(I) Compound

UV irradiation of solutions of a guanidinate coordinated dimagnesium(I) compound, [{(Priso)Mg}₂] 3 (Priso=[(DipN)₂CNPrⁱ₂]⁻, Dip=2,6-diisopropylphenyl), in either benzene, toluene, the three isomers of xylene, or mesitylene, leads to facile activation of an aromatic C−H bond of the solvent in all cases, and formation of aryl/hydride bridged magnesium(II) products, [{(Priso)Mg}₂(μ-H)(μ-Ar)] 4 – 9 . In contrast to similar reactions reported for β-diketiminate coordinated counterparts of 3 , these C−H activations proceed with little regioselectivity, though they are considerably faster. Reaction of 3 with an excess of the pyridine, p-NC₅H₄Bu^t (py^But), gave [(Priso)Mg(py^ButH)(py^But)₂] 10 , presumably via reduction of the pyridine to yield a radical intermediate, [(Priso)Mg(py^But⋅)(py^But)₂] 11 , which then abstracts a proton from the reaction solvent or a reactant. DFT calculations suggest two possible pathways to the observed arene C−H activations. One of these involves photochemical cleavage of the Mg−Mg bond of 3 , generating magnesium(I) doublet radicals, (Priso)Mg⋅. These then doubly reduce the arene substrate to give “Birch-like” products, which subsequently rearrange via C−H activation of the arene. Circumstantial evidence for the photochemical generation of transient magnesium radical species includes the fact that irradiation of a cyclohexane solution of 3 leads to an intramolecular aliphatic C−H activation process and formation of an alkyl-bridged magnesium(II) species, [{Mg(μ-Priso^−H)}₂] 12 . Furthermore, irradiation of a 1 : 1 mixture of 3 and the β-diketiminato dimagnesium(I) compound, [{(^DipNacnac)Mg}₂] (^DipNacnac=[HC(MeCNDip)₂]⁻), effects a “scrambling” reaction, and the near quantitative formation of an unsymmetrical dimagnesium(I) compound, [(Priso)Mg−Mg(^DipNacnac)] 13 . Finally, the EPR spectrum (77 K) of a glassed solution of UV irradiated 3 is dominated by a broad featureless signal, indicating the presence of a doublet radical species.     

Wilson's theorem for consensus functions on hierarchies

Wilson in 1972 gave a generalization of Arrow's theorem without the Pareto axiom. We prove a version of Wilson's theorem for consensus functions on hierarchies.