Forced proximity of nitroxide groups in pincer compounds with a xanthene spacer

We designed bisnitroxide compounds where the radical sites are located close to each other in a molecule. Two new pincer-type bisnitroxide compounds have been synthesized, involving xanthene-4,5-diyl as a spacer and tert-butyl phenyl nitroxides as arms. From the X-ray crystal structure analysis, the shortest intramolecular interatomic N?O and O?O distances respectively are 5.074(6) and 5.258(6) Å for the m,m′-derivative and 3.624(3) and 3.771(3) Å for the p,p′-derivative. The N?O distance in the latter satisfies the empirical criterion for possible dimerization/degradation reaction accompanied by dia-/paramagnetic transition. However, the magnetic study clarified paramagnetic behavior in all the temperature range. According to a singlet-triplet model, antiferromagnetic couplings were characterized with 2J/k_B = ?7.71(2) and ?8.83(4) K for the m,m′ and p,p′-derivatives, respectively. The present result suggests that a more flexible spacer is required for realization of possible dia-/paramagnetic transition.     

Structure of liquid-crystalline phases formed by N-acetyl-L-glutamic acid oligomeric benzyl esters –2H NMR study

A series of N-acetyl-L-glutamic acid oligopeptide benzyl esters with exact residue numbers 4, 6, and 12 has been synthesized by a stepwise procedure. For these oligopeptide–dioxane binary systems, the behavior of the liquid-crystalline phases has been examined␣by the use of ²H NMR, and the results indicate that highly ordered aggregates formed by these oligopeptides in dioxane are in an alignment similar to that in a nematic mesophase. Received: 27 February 2001 Accepted: 8 May 2001     

Twist bend nematic liquid crystals prepared by one-step condensation of 4-(4-Pentylcyclohexyl) benzoic acid and alkyl diol

Twist bend nematic (N_TB)-forming 9OCCHP5 and 11OCCHP5 dimers were synthesised by one-step condensation of 4-(4-pentylcyclohexyl) benzoic acid and alkyl diol with yields as high as 80%. Although each dimer formed the N_TB phase only during the cooling process in a narrow temperature width as large as 4°C, their equiweight mixture formed an N_TB phase during both the heating and cooling processes, displaying elliptical polygonal domains and rope-like optical texture. The N_TB temperature range became wider by 29–38°C and reduced the orientational order parameter significantly from 0.39 to 0.29 with decreasing temperature.     

Carbon Monoxide Oxidation by Polyoxometalate‐Supported Gold Nanoparticulate Catalysts: Activity,Stability, and Temperature‐ Dependent Activation Properties

Nanoparticulate gold supported on a Keggin‐type polyoxometalate (POM), Cs₄[α‐SiW₁₂O₄₀]?n H₂O, was prepared by the sol immobilization method. The size of the gold nanoparticles (NPs) was approximately 2 nm, which was almost the same as the size of the gold colloid precursor. Deposition of gold NPs smaller than 2 nm onto POM (Au/POM) was essential for a high catalytic activity for CO oxidation. The temperature for 50 % CO conversion was ?67 °C. The catalyst showed extremely high stability for at least one month at 0 °C with full conversion. The catalytic activity and the reaction mechanism drastically changed at temperatures higher than 40 °C, showing a unique behavior called a U‐shaped curve. It was revealed by IR measurement that Au^δ+ was a CO adsorption site and that adsorbed water promoted CO oxidation for the Au/POM catalyst. This is the first report on CO oxidation utilizing Au/POMs catalysts, and there is a potential for expansion to various gas‐phase reactions.     

The second-generation synthesis of BICMAP analogues

We previously reported the synthesis of BICMAP (1a) via 6-diphenylphosphino-2,3-dihydrobenzofuran as a key intermediate. However, we did not successfully synthesize BICMAP analogues via a similar synthetic route. Herein we report the second-generation synthesis of BICMAP and its derivatives via diethylphosphonate as a key intermediate.     

Thin-layer chromatographic behavior of rare earths on silica gel with aqueous alkaline earth metal nitrate solutions as mobile phases

The TLC behavior of all the rare earths except Pm has been surveyed on silica gel (pH 7.0) pretreated with 0.1 mol L(-1) tris(hydroxymethyl)aminomethane and 0.1 mol L(-1) HCl with aqueous nitrate solutions of alkaline earth metals as mobile phases. The RF values of the lanthanides varied in a regular and characteristic way accompanied by the tetrad effect with increasing atomic number, and when the mobile phases were changed the RF values of each metal decreased in the order Mg2+ > Ca2+ > Sr2+ > Ba2+, as the crystal ionic radii of the alkaline earth metals increased. This adsorption sequence was not observed with alkali metal nitrate and alkali metal chloride mobile phases. A brief discussion concerning the effect on RF values of the solvent cations and the adsorption mechanism is included; also presented are typical chromatograms for the separation of multi-component mixtures containing adjacent lanthanides.     

Chemical trend of Ln-M exchange couplings in heterometallic complexes with Ln = Gd, Tb, Dy, Ho, Er and M = Cu, V

The 4f-3d exchange couplings were definitively and precisely determined in the dinuclear complexes (Ln-M) involving double μ-oxo-bridges, by means of combined high-frequency electron paramagnetic resonance and pulsed-field magnetization techniques, revealing a monotonic decrease of ferromagnetic J(Ln-Cu) in the order of the atomic number, (64)Gd to (68)Er.     

A pyrazine-bridged linear pentanuclear copper(II) complex and related tri- and dinuclear complexes showing various coordination structures and magnetic couplings

Sterically bulky pyrazines have been successfully utilized for the preparation of discrete oligo-nuclear TBP (trigonal bipyramidal), SqP (square pyramidal), and Oh (octahedral) copper(II) complexes. We have synthesized a unique linear pentanuclear complex [{Cu(hfac)₂}₅(μ-2-butyl-3-methylpyrazine)₄]. The two terminal copper(II) ions have a SqP structure while the three inner ions have an Oh one. The solvent molecule was incorporated in the clearance of the lattice. From another reaction under harsh conditions, we separated [{Cu(hfac)₂}₃(μ-2-butyl-3-methylpyrazine)₂], which can be regarded as the central moiety of the pentanuclear one. We also prepared a dinuclear complex [{Cu(hfac)₂}₂(μ-tetramethylpyrazine)], in which the pyrazine nitrogen atoms were located at TBP equatorial positions. Single-crystal EPR measurements supported its compressed TBP structure. The exchange coupling was antiferromagnetic with J_TBP–TBP/k_B = −3.6 K. The linear trinuclear [{Cu(hfac)₂}₃(μ-2,3,5-trimethylpyrazine)₂], having two TBP Cu ions with an intervening Oh Cu ion, showed very weak antiferromagnetic coupling. DFT calculations on these compounds indicated that the σ-type orbital overlap between the Cu and N atoms is essential for superexchange interactions.     

Enantioselective reductive aldol reaction using tertiary amine as hydride donor

An efficient method was developed for the enantioselective reductive aldol reaction of α,β-unsaturated ketones with aldehydes in the presence of a Lewis base catalyst; conjugate reduction using a tertiary amine and trichlorosilyl triflate, followed by an aldol reaction with BINAP dioxide (BINAPO) as an organocatalyst, gave the corresponding product in high yield with high stereoselectivity.