Ru3(CO)12-catalyzed silylation of benzylic C-H bonds in arylpyridines and arylpyrazoles with hydrosilanes via C-H bond cleavage

Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively. For this silylation reaction, pyridyl and pyrazolyl groups, and the imino group in hydrazones, can function as a directing group. Several hydrosilanes involving triethyl-, dimethylphenyl-, tert-butyldimethyl-, and triphenylsilanes can be used as a silylating reagent. Coordination of an sp2 nitrogen atom to the ruthenium complex is important for achieving this silylation reaction.     

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).     

Polymers having stable radicals. II. Synthesis of nitroxyl polymers from 4-methacryloyl derivatives of 1-hydroxy-2,2,6,6-tetramethylpiperidine

Polymers having stable pendant . radicals were synthesized through their precursor polymers by oxidizing them in air or by H₂O₂–Na₂WO₄. Hydrochlorides and sulfates of 4-methacryloylamino- and 4-methacryloyloxy-1-hydroxy-2,2,6,6-tetramethylpiperidines were synthesized as precursor monomers and polymerized by using α,α′-azobisisobutyronitrile under appropriate conditions to precursor polymers of high molecular weight: poly-4-methacryloylamino-/oxy-1-hydroxy-2,2,6,6-tetramethylpiperidinehydrochlorides and sulfates. The precursor polymers were converted to polymers having nitroxyl stable radicals, i.e., poly-4-methacryloylamino-/oxy-2,2,6,6-tetramethylpiperidine-1-oxyls, by oxidation in air or with H₂O₂–Na₂WO₄ without any main-chain scission. The structure of the resultant stable radical polymers was determined by infrared, ultraviolet, and ESR spectroscopy. Based on the results of spectroscopic analysis and Kjeldahl analysis, the transformation from precursors to nitroxyl stable radical polymers was found to be quantitative. Investigations on the applicability of polymeric nitroxyl radicals to oxidation-reduction reactions were attempted by means of polarography; the reduction half-wave potential was found to be ?1.16 V for the mercury pool.     

Grafting of a bicycloorthoester onto polymers bearing sulfonium salt structures

Graft copolymerization of a bicycloorthoester (BOE) with polymer-supported sulfonium salts was studied. Several polymer-supported sulfonium salts were prepared by the homopolymerizations of p-vinylbenzyl tetramethylenesulfonium hexafluoroantimonate ( 2 ) and 4-(p-vinylphenyl)butyl tetramethylenesulfonium hexafluoroantimonate ( 3 ), and by the copolymerizations of 2 with some vinyl monomers (n-butyl vinyl ether, styrene, acrylonitrile, and p-styrenesulfonic acid potassium salt). These sulfonium salts could initiate the polymerization of BOE to give grafted polymers. Temperature dependences of the catalytic activity of them were not so dramatic as that of benzyl tetramethylenesulfonium hexafluoroantimonate ( 1 ), but the activities of them were higher than that of 1 at temperatures lower than 80°C. The conversion of BOE in the polymerizations with these polymer initiators was ca. 30–70% at 120°C for 7 h. An effect of the comonomer structure on the catalytic activity was observed and styrene was the best comonomer for 2 in terms of the reactivity of the copolymer. The spacer-modified sulfonium salt (homopolymer of 3 ) was slightly lower than polymer-supported benzyl type sulfonium salt (homopolymer of 2 ) in the catalytic activity.     

Control of viscoelasticity using redox reaction

The viscoelasticity of a fluid was tuned with the Faradaic reaction of (11-ferrocenylundecyl)trimethylammonium bromide (FTMA), a "redox-switchable" surfactant. An aqueous solution of the reduced form of FTMA exhibited a remarkable viscoelasticity in the presence of sodium salicylate (NaSal) because of the formation of three-dimensional entanglement of wormlike micelles. Electrolytic oxidation of FTMA caused the viscosity of the system to dramatically decrease and the elasticity to disappear. This drastic decrease in viscoelasticity arose from the disruption of wormlike micelles. This novel electrorheological phenomenon is expected to be applicable to ink for inkjet printers, the electrochemically controlled release of substances entrapped in wormlike micelles of FTMA, and fluid flow rate control using electric signals.     

New tridentate cyclometalated platinum(II) and palladium(II) complexes of N,2-diphenyl-8-quinolinamine: syntheses, crystal structures, and photophysical properties

A new tridentate cyclometalated platinum(II) complex derived from N,2-diphenyl-8-quinolinamine, which consists of two crystallographic independent molecules with two intermolecular N-H-Cl-Pt hydrogen bonds forming a dimer, exhibited a low-energy luminescence at ca. 740 nm in a 1 × 10⁻³ M dichloromethane solution and a strong emission centered at 670 nm in a solid state, but the analogous palladium(II) complex was nonemissive at room temperature.     

Hyperfine interactions in icosahedral quasicrystals: a Mössbauer study

Icosahedral Al₆₅Cu₂₀Fe₁₅ and Al₄₀Cu_9.9Ge₂₅Mn₂₅ ⁵⁷Fe_0.1 quasicrystals are studied using⁵⁷Fe transmission Mössbauer experiments. The spectra are analyzed by distributions of electric-quadrupole interaction accounting for line asymmetries. Temperature dependences of the hyperfine parameters derived comprising average values ofP() distributions, corresponding standard deviations and center shifts are presented in a whole range from 8 to 300 K.