Transition‐Metal Catalysis of Triene 6π Electrocyclization: The π‐Complexation Strategy Realized

Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C₅H₅)Ru(NCMe)₃]PF₆ as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition‐metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations.     

Entanglements in amorphous polymer networks

This paper consists of two parts. In the first part, the strain dependence of entanglements or constraints acting along the contour of a Gaussian chain is derived. The functional form of the elastic free energy resulting from constraints along the chain contour is identical to that obtained in the Flory constrained junction model. In the second part, the effective number of constraints acting along the contour of a chain is discussed. The choice of this number results from postulates imposed by various authors and cannot be derived by rigorous theory. The paper compares the predictions based on these assumptions with experimental data from model networks.     

Rubber elasticity in the range of small uniaxial tensions and compressions. Results for poly(dimethylsiloxane)

Results of uniaxial tension and compression experiments are reported on crosslinked polydimethylsiloxane (PDMS) networks in the unswollen state over the range 0.5 < α^?1 < 1.2 where α is the extension ratio. Curves representing the reduced force [f] = f(V⁰/V)^1/3(α – α^?2)^?1 plotted against α^?1 can be approximated by straight lines for 0.5 < α^?1 < 0.9, in agreement with the phenomenological Mooney equation. As α^?1 approaches 1, however, they tend to level off and continue into the α^?1 > 1 region with decreasing slope. These results are in agreement with the predictions of recent elasticity theories that incorporate the effect of junction-chain entanglements in the elastic free energy.     

On semigroups generated by restrictions of elliptic operators to invariant subspaces

Let A be the closed unbounded operator inL _p(G) that is associated with an elliptic boundary value problem for a bounded domainG. We prove the existence of a spectral projectionE determined by the set Γ = {λ;θ ₁≦argλ≦θ ₂} and show thatAE is the infinitesimal generator of an analytic semigroup provided that the following conditions hold: 1<p<∞; the boundary ϖΓ of Γ is contained in the resolvent setp(A) ofA;π/2≦θ<θ ₂≦3π/2 ; and there exists a constantc such that (I)││(λ-A)^-1││≦c/│λ│ for λ∈ϖΓ. The following consequence is obtained: Suppose that there exist constantsM andc such that λ∈p(A) and estimate (I) holds provided that |λ|≧M and Re λ=0. Then there exist bounded projectionE ⁻ andE ⁺ such thatA is completely reduced by the direct sum decompositionL _p(G)=E⁻L_p (G) ⊕E⁺L_p (G) and each of the operatorsAE ⁻ and—AE ⁺ is the infinitestimal generator of an analytic semigroup.     

Cross section for the H+H2O abstraction reaction: experiment and theory

The absolute value of the cross section for the abstraction reaction between fast H atoms and H2O has been determined experimentally at a mean collision energy of 2.46 eV. The OH population distribution at the same mean energy has also been determined. The new measurements are compared with state-of-the-art quantum mechanical and quasiclassical scattering calculations on the most recently developed potential energy surface.     

Minimal number of singular fibers in a Lefschetz fibration

There exists a (relatively minimal) genus Lefschetz fibration with only one singular fiber over a closed (Riemann) surface of genus iff and . The singular fiber can be chosen to be reducible or irreducible. Other results are that every Dehn twist on a closed surface of genus at least three is a product of two commutators and no Dehn twist on any closed surface is equal to a single commutator.

     

Asymmetric impacts of global risk appetite on the risk premium for an emerging market

This paper analyzes the impact of global risk appetite on the risk premium utilizing high-frequency data. Taking the Turkish economy as our laboratory, we find that the risk premium volatility responds only to a worsening in the risk appetite for the Turkish economy, which is a result that we do not observe for the other emerging markets. Then, we investigate the role of current account dynamics on this asymmetric effect, by focusing also on an economy with similar current account performance. The empirical results find supporting evidence for the role of current account dynamics on the estimated asymmetry.     

The kinetics of methane ignition in fuel-rich HCCI engines: DME replacement by ozone

Fuel-rich combustion of methane in a homogeneous-charge compression-ignition (HCCI) engine can be used as a polygeneration process producing work, heat, and useful chemicals like syngas. Due to the inertness of methane, additives such as dimethyl ether (DME) are needed to achieve ignition at moderate inlet temperatures and to control combustion phasing. Because significant concentrations of DME are then needed, a considerable part of the fuel energy comes from DME. An alternative ignition promotor known from fuel-lean HCCI is ozone (O₃). Here, a combined experimental and modelling study on the ignition of fuel-rich partial oxidation of methane/air mixtures at Φ = 1.9 with ozone and DME as additives in an HCCI engine is conducted. Experimental results show that ozone is a suitable additive for fuel-rich HCCI, with only 75 ppm ozone reducing the fuel-fraction of DME needed from 11.0% to 5.3%. Since ozone does not survive until the end of the compression stroke, the reaction paths are analyzed in a single-zone model. The simulation shows that different ignition precursors or buffer molecules are formed, depending on the additives. If only DME is added, hydrogen peroxide (H₂O₂) and formaldehyde (CH₂O) are the most important intermediates, leading to OH formation and ignition around top dead center (TDC). With ozone addition, methyl hydroperoxide (CH₃OOH) becomes very important earlier in the compression stroke under these fuel-rich conditions. It is then later converted to CH₂O and H₂O₂. Thus, ozone is a very effective additive not only for fuel-lean, but also for fuel-rich combustion. However, the mechanism differs between both regimes. Because less of the expensive additives are needed, ozone could help improving the economics of a polygeneration process with fuel-rich operated HCCI engines.