SOME PRELIMINARY INFORMATION ON SYNDIOTACTIC POLYSTYRENE CATALYSTS

Syndiotactic specific polymerization of styrene has been investigated by ~(13)C NMR analysis and isotopic laelling methods. The value of the activation energy involved in the steric control has been determined. Some information of the number of the active sites and on the life of the catalysts is reported.     

Classical and metallocene catalytic systems: Comparison between the stereochemical mechanisms of α-olefin polymerization

Classical Ziegler-Natta and Kaminsky-Ewen catalysts promoting polymerization of hydrocarbon monomers are compared considering the reactivity and the stereochemical mechanisms of polymerization. It is suggested that also the “active sites” of heterogeneous catalysts could be cationic.     

Mechanism of syndiotactic-specific polymerization of styrene

Perusal of literature data and some new results concerning syndiotactic-specific polymerization of styrene suggest a reaction mechanism accounting for the steric control. Key features of the proposed mechanism are stereorigid ηⁿ coordination of the growing chain end and diastereoselective coordination of the monomer imposed by direct interactions with the ancillary ligand of the metal complex, a pseudotetrahedral chiral Ti(III) or Zr(III) cation, which inverts its configuration after every syndiospecific insertion step.     

STM images of a large organic molecule adsorbed on a bare metal substrate or on a thin insulating layer: Visualization of HOMO and LUMO

An isomer of the methylterrylene molecule was adsorbed both on Cu(111) and on a NaCl bilayer deposited on Cu(111) and imaged by ultra high vacuum scanning tunneling microscopy at low temperature (5 K). On the bare metal surface, the STM images do not reveal any intramolecular resolution and do not depend on the applied tunnel bias. On the contrary, the images acquired at specific bias voltages for the molecule on the salt layer show a striking similarity with the spatial distribution of the electronic probability density in the highest occupied molecular orbital (HOMO) and in the lowest unoccupied molecular orbital (LUMO) of free methylterrylene. They are well reproduced by elastic scattering quantum chemistry calculations. These data provide a direct view of the hyperconjugative interaction between the methyl group and the frontier orbitals of terrylene.     

Recognizing Balanceable Matrices

A 0/±1 matrix is balanced if it does not contain a square submatrix with exactly two nonzero entries per row and per column in which the sum of all entries is 2 modulo 4. A 0/1 matrix is balanceable if its nonzero entries can be signed ±1 so that the resulting matrix is balanced. A signing algorithm due to Camion shows that the problems of recognizing balanced 0/±1 matrices and balanceable 0/1 matrices are equivalent. Conforti, Cornuéjols, Kapoor and Vušković gave an algorithm to test if a 0/±1 matrix is balanced. Truemper has characterized balanceable 0/1 matrices in terms of forbidden submatrices. In this paper we give an algorithm that explicitly finds one of these forbidden submatrices or shows that none exists. Received: October 2004     

Mikrostruktur und Schmelzpunkt von stereoregulären Polymeren. Eine vorläufige experimentelle Beziehung für isotaktisches Polypropylen

Ohne Zusammenfassung