Ethylene polymerization by chromium complexes with phosphorous‐bridged bisphenoxy ligand

Chromium catalysts combined with phosphorous‐bridged bisphenoxy ligands were found to be highly active for ethylene polymerization. The most efficient catalyst precursor among them, generated by combining bis[3‐tert‐butyl‐5‐methyl‐2‐hydroxyphenyl](phenyl)phosphine hydrochloride ( 1a ) and CrCl₃(THF)₃, was characterized. X‐ray analysis of (3‐tert‐butyl‐5‐methyl‐2‐phenoxy)(3‐tert‐butyl‐5‐methyl‐ 2‐hydroxyphenyl)(phenyl)phosphine bis(tetrahydrofuran)chromium dichloride ( 6 ), obtained by the reaction of 1a and CrCl₃(THF)₃ in the presence of NaH, revealed a unique structure in which one phenol moiety of the bisphenol did not coordinate to the chromium center. Complex 6 showed higher activities than those observed in the in situ catalyst system. Polyethylene of various molecular weights was obtained with differing activators. The highest activity (113.5 kg mmol (cat)^?1 h^?1) was observed when TIBA/TB was used as a cocatalyst. A medium molecular weight polymer with narrow molecular weight distribution (M_w = 128,700, M_w/M_n = 1.8) was obtained using a 6 ‐TIBA/B(C₆F₅)₃ system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3668–3676, 2007     

Michael addition reactions of acetoacetates and malonates with acrylates in water under strongly alkaline conditions

Michael addition reactions of acetoacetates and malonates with acrylates in a 5 M KOH aqueous solution without using any other catalysts are described. When they are either tert-butyl or benzyl esters, the reaction proceeded very rapidly to afford moderate to high yields of the corresponding bis-Michael adducts that are unexpectedly stable under these conditions.     

Rational design of CH/pi interaction sites in a basic resolving agent

A novel synthetic basic resolving agent, cis-1-aminobenz[f]indan-2-ol (ABI), was rationally designed by introducing effective CH/pi interaction sites to cis-1-aminoindan-2-ol (AI), whose chiral recognition ability has been reported from our laboratory. ABI was applicable to a wide variety of racemic arylalkanoic acids and showed moderate to excellent chiral recognition ability, which was obviously higher than that of AI. The fundamental and important role of CH/pi interactions, such as tunable CH(sp(2))/pi and CH(sp(3))/pi interactions, in the chiral recognition by ABI was revealed by X-ray crystallographic study.     

Quinolone analogues 6 [1‐5]. Synthesis of 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4(1H)‐ones

The reaction of the quinoxaline N‐oxides 7a,b with diethyl ethoxymethylenemalonate gave the 1‐methylpyridazino[3,4‐b]quinoxaline‐4,4‐dicarboxylates 8a,b , whose reaction with N‐bromosuccinimide or N‐chlorosuccinimide afforded the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxaline‐4,4‐dicarboxylates 9a‐d. The reaction of compounds 9a‐d with hydrazine hydrate resulted in hydrolysis and decarboxylation to provide the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxaline‐4‐carboxylates 10a‐d , whose reaction with nitrous acid effected oxidation to furnish the 3‐halogeno‐4‐hydroxy‐1‐methylpyridazino[3,4‐b]quinoxaline‐4‐carboxylates 11a‐d , respectively. The reaction of compounds 11a‐d with hydrazine hydrate afforded the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4‐ols 12a‐d , whose oxidation provided the 3‐halogeno‐1‐methylpyridazino[3,4‐b]quinoxalin‐4(1H)‐ones 6a‐d , respectively. Compounds 6a‐d had antifungal activities in vitro.     

Conformation and Atropisomeric Properties of Indometacin Derivatives

The stereochemistry around the N‐benzoylated indole moiety of indometacin was studied by restricting the rotation about the N? C7′ and/or C7′? C1′ bond. In the 2′,6′‐disubstituted ones, an atropisomeric property was found and the atropoisomers were separated and isolated as stable forms. Their biological abilities to inhibit cyclooxygenase‐1 (COX‐1) and cyclooxygenase‐2 (COX‐2) were examined. Only the aR‐isomer showed specific inhibition of COX‐1, and COX‐2 was not inhibited by either atropisomer. Conformational analysis in NMR studies and X‐ray crystallography, and CD spectra in combination with calculations were utilized to elucidate the bioactive conformations.     

Chiral Photoresponsive Tetrathiazoles That Provide Snapshots of Folding States

Herein, we designed chiral photoresponsive tetra(2‐phenylthiazole)s, which induce a diastereoselective 6π‐electrocyclization reaction in a helically folded structure to freeze the conformational interconversions. The folding conformation with one helical turn of tetra(2‐phenylthiazole)s was supported by multiple intramolecular noncovalent interactions including vicinal S???N interheteroatom interactions and CH–π and π–π stacking interactions between nonadjacent units, as found in X‐ray crystal structures as well as quantum chemical calculations. The introduction of a chiral group at both ends of tetra(2‐phenylthiazole) dictates the preferential folding into a one‐handed helix conformation by the simultaneous operation of S???O and multiple CH–π interactions that involve the chiral end groups. Since the tetra(2‐phenylthiazole)s possess two equivalent photoreactive 6π‐electron systems and the folded conformation is suitable for photoinduced electrocyclization reaction, they undergo a photocyclization reaction in a stereoselective manner to memorize the chirality of the helix in a resulting diastereomeric closed form.     

Geometrical Evolution and Formation of the Photoproduct in the Cycloreversion Reaction of a Diarylethene Derivative Probed by Vibrational Spectroscopy

The geometrical evolution of the reactant and formation of the photoproduct in the cycloreversion reaction of a diarylethene derivative were probed using time-resolved absorption spectroscopies in the visible to near-infrared and mid-infrared regions. The time-domain vibrational data in the visible region show that the initially formed Franck-Condon state is geometrically relaxed into the minimum in the excited state potential energy surface, concomitantly with the low-frequency coherent vibrations. Theoretical calculations indicate that the nuclear displacement in this coherent vibration is nearly parallel to that in the geometrical relaxation. Time-resolved mid-infrared spectroscopy directly detected the formation of the open-ring isomer with the same time constant as the decrease of the closed-ring isomer in the excited state minimum. This observation reveals that no detectable intermediate, in which the population is accumulated, is present between the excited closed-ring isomer and the open-ring isomer in the ground state.     

Alloyed Tetranuclear Metal Chains of Pd4−nPtn (n=0–3) Scaffolded by a New Linear Tetraphosphine Containing a PNP Bridge

A new linear tetraphosphine containing a PNP phosphazane bridge, rac-bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine (rac-dpmppan), was synthesized and utilized to support a series of Pd/Pt mixed metal tetranuclear chains, [Pd_4−nPt_n(μ-rac-dpmppan)₂(XylNC)₂](PF₆)₂ (XylNC=xylyl isocyanide; n=0: Pd₄ ( 1 ), 1: PtPd₃ ( 2 ), 2: PtPd₂Pt ( 3 ), 2: Pt₂Pd₂ ( 4 ), 3: Pt₂PdPt ( 5 )), in which the number and positions of additional Pt atoms were successfully controlled depending on the respective synthetic procedures using transformations from 1 to 3 through 2 and from 4 to 5 by redox-coupled exchange reactions. The ³¹P{¹H} NMR and ESI mass spectra and X-ray diffraction analyses revealed almost identical tetranuclear structures, with slight contraction of metal-metal bonds according to incorporation of Pt atoms. The electronic absorption spectra of 1 – 5 exhibited characteristic bands at 635–510 nm with an energy propensity depending on the number and positions of Pt centres, which were assigned to HOMO (dσ*σσ*) to LUMO (dσ*σ*σ*) transition by theoretical calculations. The present results demonstrated that the electronic structures of Pd/Pt mixed-metal tetranuclear complexes are finely tuned as orbital-overlapping alloyed metal chains by atomically precise Pt incorporation in the Pd₄ chain.     

6 j symbols for $U_q (\mathfrak{s}\mathfrak{l}_2 )$U_q (\mathfrak{s}\mathfrak{l}_2 ) and non-Euclidean tetrahedra

We relate the semiclassical asymptotics of the 6j symbols for the quantized enveloping algebra at q a root of unity (resp. q real positive) to the geometry of spherical (resp. hyperbolic) tetrahedra.     

Soft x-ray spectroscopy of Ba24Ge100: electronic phase transition and Ba-atom rattling

The electronic states of Ba24Ge100 are studied by soft x-ray photoelectron spectroscopy (XPS) at a high-energy photon factory. A large reduction in the density of states (DOS) at the Fermi level is clearly shown before and after the electronic phase transition at 200 K. The changes in the spectrum widths and the fine structures of the core-level Ba 4d spectra give a very reasonable indication of the Ba-atom rattlings in the clathrate polyhedra. On-resonance experiments using the excitation from Ba 3d to 4f levels display that the wave functions of Ba 5d and 6s orbitals give only a small contribution to make a Fermi surface through the hybridization with the Ge20 cluster orbitals. Importantly, reliable values of the DOS at the Fermi level NEF are successfully deduced, using two data sets of DOS obtained from high-resolution XPS and the total magnetic susceptibilities by a superconducting quantum interference device, to be 0.149 and 0.0427 states eV(-1) (Ge atom)(-1) for a high-temperature and for a low-temperature phase.