High-fidelity Recognition of Organotrifluoroborate Anions (R−BF3−) as Designer Guest Molecules

The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF₃⁻). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF₃⁻, by cyanostar macrocycles that are size-complementary to the inorganic BF₄⁻ progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K⁺ salts of R−BF₃⁻ anions.     

Flatness in analytic mappings I. On an announcement of Hironaka

We present a stratification by “normal flatness” associated to an analytic mapping, analogous to Hironaka's classical result for analytic spaces. Our construction is based on a generic normal flatness theorem for mappings, proved using techniques concerning the variation of modules of meromorphically parametrized formal power series [1]. The existence of such a stratification was announced by Hironaka [13], but the other claims made in [13] are false. Counterexamples are also presented here.     

Enantiodiscrimination of racemic electrophiles by diketopiperazine enolates: asymmetric synthesis of methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates

Enolates of (S)-N,N′-bis-(p-methoxybenzyl)-3-iso-propylpiperazine-2,5-dione exhibit high levels of enantiodiscrimination in alkylations with (RS)-1-aryl-1-bromoethanes and (RS)-2-bromoesters, affording substituted diketopiperazines containing two new stereogenic centres in high de. Deprotection and hydrolysis of the resultant substituted diketopiperazines provides a route to the asymmetric synthesis of homochiral methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates in high de and ee.     

Polyhedral <Emphasis Type="Italic">K</Emphasis><Subscript><Emphasis Type="Italic">2</Emphasis></Subscript>

 Using elementary graded automorphisms of polytopal algebras (essentially the coordinate rings of projective toric varieties) polyhedral versions of the group of elementary matrices and the Steinberg and Milnor groups are defined. They coincide with the usual K-theoretic groups in the special case when the polytope is a unit simplex and can be thought of as compact/polytopal substitutes for the tame automorphism groups of polynomial algebras. Relative to the classical case, many new aspects have to be taken into account. We describe these groups explicitly when the underlying polytope is 2-dimensional. Already this low-dimensional case provides interesting classes of groups. Received: 13 December 2001 / Revised version: 24 June 2002 The second author was supported by the Deutsche Forschungsgemeinschaft, INTAS grant 99-00817 and TMR grant ERB FMRX CT-97-0107 Mathematics Subject Classification (2000): 14L27, 14M25, 19C09, 52B20     

A New Asymmetric Long-Range Model and Algebraic Bethe Ansatz

A new integrable long-range model is derived from a new asymmetric R-matrix recently discussed by Bibikov in relation to a XXZ spin chain in an external magnetic field. The algebraic Bethe Ansatz is used to derive the eigenvalues and equations for the eigen momenta both for the usual and long-range model.     

Anionic iron(II) alkoxides as initiators for the controlled ring‐opening polymerization of lactide

Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(O^tBu)₃]₂ ( 1 ) and [(THF)₄Na₂Fe(2,6‐diisopropylphenolate)₄] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO₄ array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003     

Experimental characterization of hexatic smectic phases through electro-optic studies and dielectric relaxation spectroscopy

The electro-optic and complex dielectric behaviour of an antiferroelectric liquid crystal 4-(1-methylheptyloxycarbonyl)phenyl 4'-(n-butanoyloxyprop-1-oxy)biphenyl-4-carboxylate, having chiral SmC_A* and hexatic smectic phases, have been investigated. Complex dielectric permittivities were measured as a function of frequency, d.c. bias field and temperature. Spontaneous polarization was measured by the current reversal technique; tilt angle was measured under a polarizing microscope using a low frequency electric field. The electro-optic properties and dielectric behaviour of the material are compared with results obtained by DSC and polarizing optical microscopy. Dielectric relaxation processes in SmC_A* and hexatic smectic phases were determined. The dielectric strength at the SmC_A* to hexatic smectic phase transition is discussed in terms of coupling between the long range bond orientational order and smectic C director. It seems from the results of spontaneous polarization and dielectric relaxation spectroscopy that the material might possess an additional phase between the SmC_A* and hexatic smectic I* phases.