Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters

Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.     

Possible spectroscopic manifestation of the angular group induced bond alteration (AGIBA) effect in toluene

The most obvious consequence of the concept of aromaticity is the common confidence that in aromatic compounds, bond lengths do not alternate and are between typical to the single and double ones. However, in 1994, performing crystal structure investigations of substituted pyridines and their salts, Krygowski and co‐workers have discovered a very surprising angular group induced bond alteration (AGIBA) effect: It appears that some angular substituents, like methoxy or nitrozo groups, can induce bond alternation in aromatic rings. Crystal studies do not allow one to operate with liquids that are more common in organic chemistry. This paper presents the first possible evidence of spectroscopic manifestations of the AGIBA effect. Raman spectra of the liquid toluene are analyzed. It is found that instead of being single, the line corresponding to the ring breathing vibrations is clearly split by 1.0–1.4 cm^?1, thus indicating the presence of two (cis‐ and trans‐) AGIBA isomers. The energy difference between these isomers estimated in temperature dependent Raman studies is found equal to 6.68 kJ mol^?1. The low‐wavenumber line therefore corresponds to the cis‐AGIBA isomer and the high‐wavenumber line to the trans‐AGIBA isomer stabilized by the AGIBA effect. Copyright © 2007 John Wiley & Sons, Ltd.     

Magnetism in disordered magnetic Fe82−xNixCr18

The zero field μSR-method has been used to study the magnetism in the disordered magnetic alloy Fe_82−xNi_xCr₁₈ near the three-critical, pointx=25. The dynamic and static local field distributions are analyzed. The difference between spin-glass states obtained either from the paramagnetic or after the double transition is discussed.     

Solving a Two-Dimensional Telegraph Equation with Anisotropic Parameters

We solve a two-dimensional telegraph equation with anisotropic parameters, which models the propagation of electromagnetic waves in the Earth–ionosphere waveguide, in the frequency range 0.1-30 Hz. The results are generalized to allow for the Earth's sphericity and the horizontal inhomogeneity of the waveguide. It is shown that the resonance character of reflection from the ionosphere at frequencies below 10 Hz becomes pronounced for the horizontal magnetic-field components and for the vertical electric-field component of a horizontal dipole. In the case of low solar activity under nighttime conditions, the oscillations in the frequency dependences of the field components are much more pronounced compared with the case of high solar activity.     

Noncommutative algebras related with Schubert calculus on Coxeter groups

For any finite Coxeter system (W,S) we construct a certain noncommutative algebra, the so-called bracket algebra, together with a family of commuting elements, the so-called Dunkl elements. The Dunkl elements conjecturally generate an algebra which is canonically isomorphic to the coinvariant algebra of the Coxeter group W. We prove this conjecture for classical Coxeter groups and I₂(m). We define a “quantization” and a multiparameter deformation of our construction and show that for Lie groups of classical type and G₂, the algebra generated by Dunkl’s elements in the quantized bracket algebra is canonically isomorphic to the small quantum cohomology ring of the corresponding flag variety, as described by B. Kim. For crystallographic Coxeter systems we define the so-called quantum Bruhat representation of the corresponding bracket algebra. We study in more detail the structure of the relations in B_n-, D_n- and G₂-bracket algebras, and as an application, discover a Pieri-type formula in the B_n-bracket algebra. As a corollary, we obtain a Pieri-type formula for multiplication of an arbitrary B_n-Schubert class by some special ones. Our Pieri-type formula is a generalization of Pieri’s formulas obtained by A. Lascoux and M.-P. Schützenberger for flag varieties of type A. We also introduce a super-version of the bracket algebra together with a family of pairwise anticommutative elements, the so-called flat connections with constant coefficients, which describes “a noncommutative differential geometry on a finite Coxeter group” in the sense of S. Majid.     

On a theorem of Marcinkiewicz and Zygmund

Let {ϕn(x)} be an orthonormal system on the closed interval [0,1], and let ∥ϕ _n ∥_∞ ≤M _n . In 1937 Marcinkiewicz and Zygmund obtained an estimate of the norm inL _q [0,1] of the sum of the series ∑ _n=1 ^∞ c _n ϕ _n (x) under the condition that {M _n } is monotone increasing. In this paper it is shown that this condition cannot be discarded. Translated fromMatematicheskie Zametki, Vol. 63, No. 3, pp. 386–390, March, 1998. The author wishes to thank V. I. Kolyada for setting the problem and for his permanent attention to this work.     

Solvent effect on reaction rates in molten salts

Predominant solvation of activated complex is shown to be characteristic for chemical and electrochemical reactions in molten salts.

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Presented at EUCHEM Conference on Molten Salts, September 2–8, 1990, Rio-Patras, Greece     

Synthesis of 6-arylspiro[tetrahydropyran-3,1′-cyclobutane]-2,4-diones

Methyl 1-(2-bromo-2-methyl-1-oxopropyl)-, 1-(1-bromocyclopentylcarbonyl)-, and 1-(1-bromocyclohexylcarbonyl) cyclobutanecarboxylates reacted with zinc and aromatic aldehydes to give, respectively, 7-aryl-2,2-dimethyl-6-oxaspiro[3.5]nonane-5,9-diones, 11-aryl-12-oxadispiro[3.1.4.3]tridecane-5,13-diones, and 12-aryl-13-oxadispiro[3.1.5.3]tetradecane-5,14-diones.