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.     

Investigation of proton conductivity of anhydrous proton exchange membranes prepared via grafting vinyltriazole onto alkaline‐treated PVDF

This work uses a simple “grafting through” approach in the preparation of anhydrous poly(vinylidene fluoride) (PVDF)‐g‐PVTri polymer electrolyte membranes (PEMs). Alkaline‐treated PVDF was used as a macromolecule in conjunction with vinyltriazole in the graft copolymerization. The obtained polymer was subsequently doped with triflic acid (TA) at different stoichiometric ratios with respect to triazole units and the anhydrous PEMs (PVDF‐g‐PVTri‐(TA)_x) were prepared. All samples were characterized by FTIR and ¹H NMR. The composition of PVDF‐g‐PVTri was determined by energy dispersive spectroscopy. Thermal properties of the membranes were examined by thermogravimetric analysis and differential scanning calorimetry. The surface roughness and morphology of the membranes were studied using atomic force microscopy, X‐ray diffraction, and scanning electron microscopy. PVDF‐g‐PVTri‐(TA)₃ (C3‐TA₃) with a degree of grafting of 47.22% showed a maximum proton conductivity of 0.09 S cm^?1 at 150 °C and anhydrous conditions. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1885–1897     

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.     

A NOTE ON GENERALIZED ABSOLUTE SUMMABILITY FACTORS FOR A TRIANGULAR MATRIX

In this paper, a general theorem on | A, δ |k -summability factors of infinite series is proved under different conditions.     

On general summability factor theorem of infinite series

A lower triangular matrix with nonzero principal diagonal entries is called a triangle. In this paper we obtain the sufficient conditions for ∑a_nλ_n to be summable ∣A∣_k whenever ∑a_n is summable ∣T∣_k for a triangle T.     

Two valued measure and some new double sequence spaces in 2-normed spaces

The purpose of this paper is to introduce some new generalized double difference sequence spaces using summability with respect to a two valued measure and an Orlicz function in 2-normed spaces which have unique non-linear structure and to examine some of their properties. This approach has not been used in any context before.     

Exact solution for in-plane static problems of circular beams made of functionally graded materials

Exact analytical solutions of in-plane static problems of circular beams with uniform cross-section made of functionally graded material (FGM) are obtained. Material properties are assumed to be varying arbitrarily through the thickness. The effects of axial extension and shear deformations are considered. The differential equation system is solved exactly using the initial values method. The circumferential stress distribution on the cross-section is also obtained. The results are compared with those of rather complex approaches in the literature, such as elasticity approach, and the comparison shows an excellent agreement. Effects of power law exponent and radius-to-height ratio of the beam on circumferential stress distribution and displacements are investigated.     

Thermal entanglement in the mixed three-spin XXZ Heisenberg model on a triangular cell

We numerically investigate the thermal entanglements of spins （1/2, 1） and spins （1/2, 1/2） in the three-mixed （1/2, 1, 1/2） anisotropic Heisenberg XXZ spin system on a simple triangular cell under an inhomogeneous magnetic field. We show that the external magnetic field induces strong plateau formation in the pairwise thermal entanglement for fixed parame-ters of the Hamiltonian in the cases of ferromagnetic and antiferromagnetic interactions. We also .observe an unexpected critical point at finite temperature in the thermal entanglement of spins （1/2, 1） for the antiferromagnetic case, while the entanglement of spins （1/2, 1） in the ferromagnetic case and the entanglement of spins （1/2, 1/2） in both ferromagnetic and antiferromagnetic cases almost decay exponentially to zero with increasing temperature. The critical point in the en-tanglement of spins （1/2, 1） in the antiferromagnetic case may be a signature of the quantum phase transition at finite temperature.     

Synthesis and characterization of mid‐ and end‐chain functional telechelics by controlled polymerization methods and coupling processes

Well‐defined polystyrene‐ (PSt) or poly(ε‐caprolactone) (PCL)‐based polymers containing mid‐ or end‐chain 2,5 or 3,5‐ dibromobenzene moieties were prepared by controlled polymerization methods, such as atom transfer radical polymerization (ATRP) or ring opening polymerization (ROP). 1,4‐Dibromo‐2‐(bromomethyl)benzene, 1,3‐dibromo‐5‐(bromomethyl)benzene, and 1,4‐dibromo‐2,5‐di(bromomethyl)benzene were used as initiators in ATRP of styrene (St) in conjunction with CuBr/2,2′‐bipyridine as catalyst. 2,5‐Dibromo‐1,4‐(dihydroxymethyl)benzene initiated the ROP of ε‐caprolactone (CL) in the presence of stannous octoate (Sn(Oct)₂) catalyst. The reaction of these polymers with amino‐ or aldehyde‐functionalized monoboronic acids, in Suzuki‐type couplings, afforded the corresponding telechelics. Further functionalization with oxidable groups such as 2‐pyrrolyl or 1‐naphthyl was attained by condensation reactions of the amino or aldehyde groups with low molecular weight aldehydes or amines, respectively, with the formation of azomethine linkages. Preliminary attempts for the synthesis of fully conjugated poly(Schiff base) with polymeric segments as substituents, by oxidative polymerization of the macromonomers, are presented. All the starting, intermediate, or final polymers were structurally analyzed by spectral methods (¹H NMR, ¹³C NMR, and IR). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 727–743, 2006     

On |A|k summability factors

Summary The paper deals with absolute summability factors for infinite series. The main result obtained in this paper generalizes a recent paper of Mazhar.