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1.
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.  相似文献   
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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.  相似文献   
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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 bn ≠ 0, rn , and rn+1 > rn. The degree of approximation by the polynomial (1 + b1zr1) · · · (1 + bnzrn) is also considered.  相似文献   
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In this paper we explicitly construct local ν-Euler derivations , where the ξα are local, conformally symplectic vector fields and the are formal series of locally defined differential operators, for Fedosov star products on a symplectic manifold (M,ω) by means of which we are able to compute Deligne's characteristic class of these star products. We show that this class is given by , where is a formal series of closed two-forms on M the cohomology class of which coincides with the one introduced by Fedosov to classify his star products. Moreover, we consider star products that have additional algebraic structures and compute the effect of these structures on the corresponding characteristic classes of these star products. Specifying the constituents of Fedosov's construction we obtain star products with these special properties. Finally, we investigate equivalence transformations between such special star products and prove existence of equivalence transformations being compatible with the considered algebraic structures. Dedicated to the memory of Moshé Flato Received: 28 June 1999 / Accepted: 11 April 2002?Published online: 11 September 2002  相似文献   
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TiCx-PECVD-layers were characterized by TEM. EDX analysis and electron diffraction. TiCx-layers deposited using benzene showed a columnar structure, at which the column size decreases with rising excess carbon content. TiCx-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.  相似文献   
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Capillary GC on permethyl α-, β-, and γ-cyclodextrins has been applied to separate and quantify the enantiomers of some 2,3-iso-propylidene-1,2,3-cyclohexanetriol derivatives. Quantitative CGC data are compared to those obtained with chiral shift 1H NMR.  相似文献   
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