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.     

Development of a quantitative FI-MS technique for the characterization of high- and nonboiling saturated hydrocarbon mixtures

Summary Using a saturated non-boiling hydrocarbon mixture, the influence of two parameters on the results of field ionization mass spectrometry (FI-MS) measurements was studied: (a) the potential difference between the FI emitter and the counterelectrode; (b) the emitter temperature.Variation of the potential difference had only a minor effect on the average molecular mass measured and had no evident effect on the relative ring number distribution in the sample. In contrast, when the emitter temperature was increased, higher average molecular masses were recorded. Moreover, the average molecular masses shifted to higher ring numbers. In order to control the relationship between the described influences during mixture analysis, measuring instructions have been developed that enable the quantitative analysis of unknown saturated samples. However, average molecular mass of the mixture must be known.

---

Entwicklung einer quantitativen FI-MS-Methode zur Charakterisierung von gesättigten hoch- und nichtsiedenden Kohlenwasserstoffgemischen

     

Kreiszylindrische Behälter auf nachgiebiger Unterlage

Ohne Zusammenfassung     

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.     

A Practical Solution to a Cargo Loading Problem at Bethlehem Steel

The optimum assignment of structural steel shapes to rail cars is an important logistical problem in the steel industry. In this paper, we discuss an application at Bethlehem Steel that not only involves weight and dimensional constraints, but also customer unloading constraints. The formulation is a generalized bin packing problem which is solved by modifying and extending the first fit decreasing algorithm. The solution algorithm, SOLID (for Structural Optimal Loading IDentification), has been used extensively for one of Bethlehem's high tonnage customers providing very good practical (implementable) results that achieve the desired goals. Bethlehem has enhanced this approach for use with other customers.     

Generalized Physical and SRB Measures for Hyperbolic Diffeomorphisms

In this paper we introduce the notion of generalized physical and SRB measures. These measures naturally generalize classical physical and SRB measures to measures which are supported on invariant sets that are not necessarily attractors. We then perform a detailed case study of these measures for hyperbolic Hènon maps. For this class of systems we are able to develop a complete theory about the existence, uniqueness, finiteness, and properties of these natural measures. Moreover, we derive a classification for the existence of a measure of full dimension. We also consider general hyperbolic surface diffeomorphisms and discuss possible extensions of, as well as the differences to, the results for Hènon maps. Finally, we study the regular dependence of the dimension of the generalized physical/SRB measure on the diffeomorphism. For the proofs we apply various techniques from smooth ergodic theory including the thermodynamic formalism. 2000 Mathematics Subject Classification. Primary: 37C45, 37D20, 37D35, Secondary: 37A35, 37E30