Preparation and properties of molybdenum and tungsten dinitrogen complexes : `XVI. Electrochemical properties of tungsten and molybdenum diazoalkane complexes

Diazoalkane complexes of type [MF(NNCRR′)(dpe)₂][BF₄] (M = Mo or W; dpe = Ph₂PCH₂CH₂PPh₂), which are easily derived from bis(dinitrogen) complexes [M(N₂)₂(dpe)₂], undergo consecutive one- and two-electron oxidations and reductions under voltammetric conditions at a platinum electrode. The ESR spectra of the species generated by the controlled potential electrolysis show that primary oxidation occurred on the metal atom (M = Mo) and reduction on the two nitrogen atoms in the diazoalkane ligands (M = Mo or W).     

Generation and detection of the radical cation and the dication derived from 4,9‐diethyl[1,4]dihydrodithiino[5,6‐f]benzotrithiole and its 5‐oxide

4,9‐Diethyl[1,4]dihydrodithiino[5,6‐f]benzotrithiole (DTBT) gave a radical cation, DTBT(•+), and a dication, DTBT(2+), on treatment with a single‐electron oxidizing reagent. Both compounds showed an ESR signal, whereas the dication, generated by this procedure, was silent for ¹H NMR. Hydrolysis of DTBT(2+) gave DTBT 1‐oxide (DTBT 1‐O) and 2‐oxide (DTBT 2‐O) together with DTBT and a mixture of several dioxides. A singlet‐state dication, DTBT(2+)‐S, which was generated upon treatment of DTBT 5‐oxide (DTBT 5‐O) with concentrated D₂SO₄, was detected by ¹H and ¹³C NMR. After 20 h, the NMR signals disappeared while the solution was active for ESR. The results suggest that (i) a species generated from DTBT by oxidation with the single‐electron oxidizing reagent is a triplet‐state dication, DTBT(2+)‐T, and (ii) DTBT(2+)‐S, initially generated, gradually isomerizes to DTBT(2+)‐T in the solution, and DTBT(2+)‐T forms a partial spin pair. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:394–401, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20445     

Direction control of chemical wave propagation in self-oscillating gel array

A chemomechanical actuator utilizing a reaction-diffusion wave across gap junction was constructed toward a novel mircoconveyer by micropatterned self-oscillating gel array. Unidirectional propagation of the chemical wave of the Belousov-Zhabotinsky (BZ) reaction was induced on gel arrays. In the case of using a triangle-shaped gel as an element of the array, the chemical wave propagated from the corner side of the triangle gel to the plane side of the other gel (C-to-P) across the gap junction, whereas it propagated from the plane side to the corner side (P-to-C) in the case of the pentagonal gel array. Numerical analysis based on the Keener-Tyson model was done for understanding the mechanism of unidirectional propagation in triangle and pentagonal gel arrays. The swelling and deswelling changes of the gels followed the unidirectional propagation of the chemical wave.     

A Unified Strategy for Exceptionally High Diastereoselectivity in the Photochemical Ring Closure of Chiral Diarylethenes

Into my arms : Photochemical cyclization of diarylethenes that have two chiral side arms showed up to 100 % de (see scheme). Introduction of these chiral side arms onto the carbon atoms where ring closure occurs is a general strategy for the highly diastereoselective cyclization of diarylethenes.

     

Guerbet reaction of primary alcohols leading to beta-alkylated dimer alcohols catalyzed by iridium complexes

[IrCl(cod)]2 and [Cp*IrCl2]2 complexes catalyzed efficiently the Guerbet reaction of primary alcohols to beta-alkylated dimer alcohols in good yields. For instance, the reaction of 1-butanol in the presence of [Cp*IrCl2]2 (1 mol %), t-BuOK (40 mol %), and 1,7-octadiene (10 mol %) produced 2-ethyl-1-hexanol in 93% yield. Various primary alcohols undergo the Guerbet reaction under the influence of Ir complexes to give the corresponding dimer alcohols in good yields. This method provides an alternative direct route to beta-alkylated primary alcohols which are prepared by aldol condensation of aldehydes followed by hydrogenation.     

Drug-plasma protein binding assay by electrokinetic chromatography-frontal analysis

We developed a rapid, microscale and reliable analytical method for binding of drugs to plasma proteins using capillary electrophoresis (CE) with ionic cyclodextrins (CD) combined with frontal analysis. These CDs were used as pseudostationary phases of electrokinetic chromatography (EKC). The CD-modified EKC (CDEKC) approach allowed us to separate anionic drugs from plasma proteins, whereas CZE could not separate these drugs from plasma proteins because they had a similar mobility like plasma proteins. CDs uniquely interact with these drugs but not with plasma proteins. Therefore, CDEKC could be coupled with frontal analysis to measure the binding of anionic drugs to plasma proteins. The binding values obtained by CDEKC were highly consistent with those determined by the ultrafiltration method. Our CDEKC approach should expand the applicability of CE to protein binding analysis.     

Langmuir-Blodgett films of a clay mineral and ruthenium(II) complexes with a noncentrosymmetric structure

Mono- and multilayers of amphiphilic [Ru(phen)(2)(dcC12bpy)](2+) (phen = 1,10-phenanthroline, dcC12bpy = 4,4'-caboxyl-2,2'-bipyridyl didodecyl ester) hybridized with a clay mineral have been prepared by a modified Langmuir-Blodgett method, and their structures and properties have been investigated. Formation of a hybrid monolayer of the Ru(II) complex cations and the clay platelets at an air-clay suspension interface was confirmed by surface pressure-molecular area (pi-A) isotherm measurement and atomic force microscopic (AFM) observation. Multilayers were fabricated by depositing the hybrid monolayers onto glass substrates. The absorbance at 492 nm due to the Ru(II) complex cation in the multilayer increased linearly with the increase in the layer number, indicating layer-by-layer deposition of the hybrid monolayers. Because no increase in the second-harmonic generation (SHG) signal from the multilayers against the layer number was observed, the orientation of the Ru(II) complex cations in the layer would be disturbed. The hydrophilic surface of the transferred hybrid monolayer can be converted to a hydrophobic surface by dipping it in an aqueous solution of octadecylammonium chloride (ODAH(+)Cl(-)). The multilayers modified with ODAH(+) showed a quadratic relation between the SHG intensity and the layer number. This means that the Ru(II) complex cations in the multilayer are successfully oriented in a noncentrosymmetric way by the conversion of the surface property. Both a racemic mixture and an enantiomer of the Ru(II) complex cations were employed to examine the chiral effect on the film properties. The chiral contribution to the SHG signal was enhanced in the multilayer modified with ODAH(+).     

Enantioselective addition of ketene silyl acetals to nitrones catalyzed by chiral titanium complexes. Synthesis of optically active beta-amino acids

A chiral titanium complex, Ti(O-i-Pr)(4)/BINOL/tert-butylcatechol, catalyzes enantioselective addition reaction of ketene silyl acetals to nitrones to give optically active beta-amino acid derivatives which are biologically active compounds and useful synthetic intermediates of natural products and pharmaceuticals such as beta-lactam antibiotics. The combined process of catalytic oxidation of secondary amines and enantioselective carbon-carbon bond formation of nitrones thus obtained with ketene silyl acetals provides a useful two-step method for the synthesis of optically active beta-amino acid derivatives and related nitrogen compounds.     

Highly Selective Copper‐Catalyzed Hydroboration of Allenes and 1,3‐Dienes

The highly selective copper‐catalyzed hydroboration of allenes has been developed. Allylboranes and alkenylboranes were selectively prepared by the judicious choice of catalytic species (copper hydride and boryl copper). Furthermore, two types of alkenylboranes could be selectively synthesized by the choice of an appropriate ligand. Mechanistic studies confirmed that the protonation of a (Z)‐σ‐allyl copper species, which was isolated and structurally characterized by single‐crystal X‐ray diffraction, was a key step in these reactions. Besides allenes, this method is also applicable to the selective hydroboration of 1,3‐diene derivatives to afford allylboranes and homoallylboranes.     

Manganese(II) o ctacyanotungstate(V)-based magnet containing a noncoordinated aromatic molecule

We have prepared a pillared layer magnetic material containing a noncoordinated aromatic molecule, [{MnII(pyrimidine)(H2O)}2{MnII(H2O)2}{WV(CN)8}2](pyrimidine)2.2H2O. This compound has one-dimensional channels (6.2 x 2.1 A) that are occupied by noncoordinated pyrimidine. The magnetization versus temperature plots showed the magnetic phased transition temperature (TC) was 47 K. The magnetization versus external magnetic field plots showed that the saturation magnetization (MS) value was 13.0 muB at 2 K. This MS value indicates that an antiferromagnetic interaction operates between the WV (S = 1/2) and MnII (S = 5/2) ions. The magnetic hysteresis loop showed that the coercive field (HC) was 17 G at 2 K.