Synthesis and Systematic Structural Analysis of Cationic Half-Sandwich Ruthenium Chalcogenocarbonyl Complexes

Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H₂IMes)(CNCH₂Ts)][BAr^F₄] (Cp=η⁵-C₅H₅⁻; H₂IMes=1,3-dimesitylimidazolin-2-ylidene; Ar^F=3,5-(CF₃)₂C₆H₃). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O<S<Se<Te. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability.     

Enantioselective Total Synthesis of (+)-Nordasycarpidone, (+)-Dasycarpidone,and (+)-Uleine

The structure of uleine type alkaloids is characterized by the presence of a bridged tetracyclic hexahydro-1H-1,5-methanoazocino[4,3-b]indole ring system 1 . Various strategies have been developed to access this polycyclic structural motif. We report herein a one-step conversion of appropriately functionalized 1,3,4-trisubstituted cyclopent-1-ene to 1 by way of an integrated oxidation/reduction/cyclization (iORC) process. This domino sequence, initiated by oxidative cleavage of cyclopentene ring, generated subsequently a cyclohexenone, an indole and a 1,3-bridged piperidine ring through formation of one C−C and two C−N bonds. Compound 1 is subsequently converted to nordasycarpidone, dasycarpidone and uleine. The chirality of the molecule was introduced by enzymatic desymmetrization of commercially available meso cis-3,5-diacetoxy-1-cyclopentene.     

Effective Synthesis of N‐Arylformamide from α‐Halo‐N‐arylacetamides

A convenient synthetic method for N‐arylformamide derivatives was successfully developed by reacting α‐iodo‐N‐arylacetamides with formamide. This method was applicable to α‐iodo‐N‐arylacetamide substrates bearing electron‐donating or electron‐withdrawing groups, N‐(benzo[d][1,3]dioxol‐5‐yl)‐2‐iodoacetamide, 2‐iodo‐N‐(pyridin‐2‐yl)acetamide, and 2‐iodo‐N‐(naphthalen‐4‐yl)acetamide to give the corresponding N‐arylformamides in moderate to excellent yields (65–94%). A plausible mechanism was proposed to account for the new transformation.     

Upgrade of beamline BL08B at Taiwan Light Source from a photon‐BPM to a double‐grating SGM beamline

During the last 20 years, beamline BL08B has been upgraded step by step from a photon beam‐position monitor (BPM) to a testing beamline and a single‐grating beamline that enables experiments to record X‐ray photo‐emission spectra (XPS) and X‐ray absorption spectra (XAS) for research in solar physics, organic semiconductor materials and spinel oxides, with soft X‐ray photon energies in the range 300–1000 eV. Demands for photon energy to extend to the extreme ultraviolet region for applications in nano‐fabrication and topological thin films are increasing. The basic spherical‐grating monochromator beamline was again upgraded by adding a second grating that delivers photons of energy from 80 to 420 eV. Four end‐stations were designed for experiments with XPS, XAS, interstellar photoprocess systems (IPS) and extreme‐ultraviolet lithography (EUVL) in the scheduled beam time. The data from these experiments show a large count rate in core levels probed and excellent statistics on background normalization in the L‐edge adsorption spectrum.     

Certain basic issues in finite-deformation continuum plasticity

Summary I consider the kinematical implications embedded in the decomposition of the deformation gradient F into two constituents, F^* (say, elastic) and F^p (say, plastic), in the form F=F^* F^p. Whatever the origin, nature, and physical meaning of these three deformation gradients, the decomposition can always be recast in the form F==V^* Q U^p, where V^* and U^p are stretch tensors, respectively associated with F^* and F^p, and Q is a unique rotation tensor. It then follows that the (elastic) spin associated with V^* and the (plastic) spin associated with U^p are fully defined by their corresponding deformation rates. I give explicit expressions defining elastic and plastic spins in terms of the elastic and plastic deformation rates, respectively. I show that, if the total velocity gradient and either the elastic or the plastic (but not both) deformation rate tensor, are given, then all the remaining kinematical rate quantities can be calculated explicitly, with no constitutive or other assumptions. I give explicit expressions for the rate of change of V^*, Q, and U^p, from which these quantities can be incrementally but directly obtained. In particular, I give explicit expressions for the elastic spin, plastic spin, and the rigid spin. Constitutive implications of these purely kinematical results are briefly discussed in connection with rate-independent and rate-dependent phenomenological elastoplasticity, and, particularly, kinematical hardening.

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Sommario Si considerano le implicazioni cinematiche insite nella decomposizione del gradiente di deformazione F in due componenti, F^* (per esempio, la parte elastica) ed P^p (per esempio, la parte plastica), nella forma F=F^*F^p. Qualunque sia l'origine, la natura e il significato fisico di questi tre gradienti, la decomposizione si può sempre riscrivere nella forma F=U^* Q U^p, in cui V^* ed U^p sono tensori di deformazione associati rispettivamente con F^* ed F^p, e Q è un tensore di rotazione univocamente definito. Ne segue che lo spin (elastico) associato con U^* e lo spin (plastico) associato con U^p sono completamente definiti dalle corrispondenti derivate delle deformazioni: di questa dipendenza si forniscono le espressioni esplicite. Si mostra quindi che, se sono dati il gradiente della velocità totale e il tensore delle deformazioni elastiche o quello delle deformazioni plastiche (ma non entrambi), tutte le altre quantità cinematiche possono essere calcolate esplicitamente, senza alcuna ulteriore ipotesi, neanche sulla legge costitutiva. Si forniscono ancora espressioni per i gradienti di V^*, Q ed U^p, dalle quali queste quantità si possono ottenere direttamente, per incrementi successivi: in particolare, si danno espressioni esplicite per lo spin elastico, plastico e rigido. Si discutono brevemente le implicazioni costitutive di questi risultati puramente cinematici, in connessione con vari aspetti fenomenologici dell'elasto-plasticità, e in particolare l'incrudimento cinematico.

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Invited Lecture presented at New Developments in Structural Mechanichs, International Meeting in memory of Professor Manfredi Romano; Catania, Italy, 4–6 July 1990.     

Cloud dispersion models

A new technique has been developed to compute mean and fluctuating concentrations in complex turbulent flows. An initial distribution of material is discretised into any small clouds which are advected by a combination of the mean flow and large scale turbulence. The turbulence can be simulated either by Kinematic Simulation or by a stochastic model for the motion of each cloud centroid. The clouds also diffuse relative to their centroids; the statistics for this are obtained from a separate calculation of the growth of individual clouds in small scale turbulence, generated by Kinematic Simulation. The ensemble of discrete clouds is periodically rediscretised, to limit the size of the small clouds and prevent overlapping. The model is illustrated with simulations of dispersion in uniform flow and in a coastal flow, and the results are compared with analytic, steady state solutions where available.     

Dispirocycles: Platforms for the Construction of High-Performance Host Materials for Phosphorescent Organic Light-Emitting Diodes

Spirocyclic compounds such as 9,9′-spirobifluorene (SBF) are becoming more and more attractive for use as host materials in organic optoelectronic devices. Herein, two dispirocycles, namely, dispiro[fluorene-9,9′-anthracene-10′,9′′-fluorene] and 10,10′′-diphenyl-10H,10′′H-dispiro[acridine-9,9′-anthracene-10′,9′′-acridine], were used for the construction of host materials 1 – 4 . The attached triphenylamino group determines the thermal, photophysical, electrochemical, and charge-transport properties, and therefore they have different electroluminescent performances. The device based on dispiro[fluorene-9,9′-anthracene-10′,9′′-fluorene] ( 2 ) and 10,10′′-diphenyl-10H,10′′H-dispiro[acridine-9,9′-anthracene-10′,9′′-acridine] ( 3 ) molecular platforms exhibited external quantum efficiencies of greater than 21 % with a very high power efficiency (≈100 lm W⁻¹). These results demonstrate the potential of extending the application of dispirocyclic molecular platforms with inherent rigidity for developing highly efficient host materials for organic light-emitting diodes.     

Integrating Biomass into the Organonitrogen Chemical Supply Chain: Production of Pyrrole and d-Proline from Furfural

Production of renewable, high-value N-containing chemicals from lignocellulose will expand product diversity and increase the economic competitiveness of the biorefinery. Herein, we report a single-step conversion of furfural to pyrrole in 75 % yield as a key N-containing building block, achieved via tandem decarbonylation–amination reactions over tailor-designed Pd@S-1 and H-beta zeolite catalytic system. Pyrrole was further transformed into dl -proline in two steps following carboxylation with CO₂ and hydrogenation over Rh/C catalyst. After treating with Escherichia coli, valuable d -proline was obtained in theoretically maximum yield (50 %) bearing 99 % ee. The report here establishes a route bridging commercial commodity feedstock from biomass with high-value organonitrogen chemicals through pyrrole as a hub molecule.