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.     

Nonlinear frequency response analysis: a recent review and perspectives

The nonlinear frequency response analysis (NFRA) can be seen as an extension of electrochemical impedance spectroscopy. NFRA gives a full and detailed representation of the system response and can establish a connection between model parameters and the experimentally observed phenomena. In this article, different theoretical NFRA approaches and the most recent application examples are discussed. A simple electrochemical example is used to showcase the benefits and disadvantages of analyzing the system response by using different approaches. In addition, it was shown how to extract experimental harmonic values and analyze them.     

Rational Functions with Prescribed Global and Local Minimizers

A family of multivariate rational functions is constructed. It has strong local minimizers with prescribed function values at prescribed positions. While there might be additional local minima, such minima cannot be global. A second family of multivariate rational functions is given, having prescribed global minimizers and prescribed interpolating data.     

Thermodynamic study of a series lithium β-diketonates

Thermal behaviour of a series of lithium β-diketonates: Li(dpm) (dpm=dipivaloylmethanate (2,2,6,6-tetramethylheptane-3,5- dionate)), Li(pta) (pta=pivaloyltrifluoracetonate (2,2-dimethyl-6,6,6-trifluoro-3,5-hexanedionate)), Li(tfa) (tfa=trifluoracetylacetonate (1,1,1-trifluoro-2,4-pentandionate)), Li(hfa) (hfa=hexafluoracetylacetonate (1,1,1,5,5,5-hexafluoro-2,4-pentandionate)) has been investigated. Gas phase composition of these complexes has been established. Temperature dependences of vapor pressure of lithium compounds were obtained by static and dynamic methods, and thermodynamic parameters were calculated. Dependence of compound volatility on ligand structure is shown. For Li(dpm) detailed investigation has been done by differential scanning calorimetry (DSC).     

Infinite products for power series

An algorithm is introduced and shown to lead to a unique infinite product representation for a given formal power series A(z) with A(0) = 1. The infinite product is , where all b_n ≠ 0, r_n , and r_n+1 > r_n. The degree of approximation by the polynomial (1 + b₁z^r₁) · · · (1 + b_nz^r_n) is also considered.     

TEM investigations on PECVD-titanium carbide layers

TiC_x-PECVD-layers were characterized by TEM. EDX analysis and electron diffraction. TiC_x-layers deposited using benzene showed a columnar structure, at which the column size decreases with rising excess carbon content. TiC_x-layers deposited using n-heptane presented a lamellar structure, at which the lamellar thickness diminishes with an increasing excess carbon content. In dependence on the layer thickness a periodic progress of the element contents was observed, at which a maximum for Ti and Cl correlates with a minimum for C. It was found that the incorporated chlorine is bonded to titanium. The lattice parameter depends on the chlorine content. Using TiCl₄/H₂/Ar-gas mixtures without any hydrocarbon, layers containing TiH₂ are formed.