Intramolecular cyclization of N‐hetarylphosphinimidic isocyanates in the synthesis of 1,7‐dihydro‐4H‐imidazo[4,5‐d][1,3,2]diazaphosphinin‐4‐one (2‐phosphapurine)

It has been found that N‐(4‐imidazolyl)phosphinimidic isocyanates obtained by the reaction of the corresponding chlorophosphine N‐hetarylimide with alkali metal cyanates can undergo intramolecular heterocyclization to yield previously unknown phosphapurine derivatives containing an endocyclic PN double bond. This radically novel approach to building the 2‐phosphapurine system shows promise for the synthesis of related phosphorus‐containing fused heterocycles. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:453–455, 2010; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20617     

Highly efficient oxidation of alcohols by the system "hydrogen peroxide-[lmn(o)3mnl](pf6)2 (l = 1,4,7-trimethyl-1,4,7-triazacyclononane)-oxalic acid"

Summary The dinuclear manganese(IV) complex [LMn(O)₃MnL](PF₆)₂ (1, L = 1,4,7-trimethyl-1,4,7-triazacyclononane) catalyzes the extremely efficient oxidation of alcohols with hydrogen peroxide at room temperature. Oxalic acid is an obligatory co-catalyst. The oxidation of isopropanol, for example, yields acetone with turnover numbers up to 40000 after 5-10 h in the absence of a solvent. 2-Cyanoethanol was oxidized by this system with somewhat lower efficiency (conversion 70%). The catalytically active cation from salt 1 was obtained in an insoluble form containing a heteropoly anion [Mn₂O₃(TMTACN)₂]₂[SiW₁₂O₄₀]. Oxidation of 2-cyanoethanol using this heterogenized catalyst and oxalic acid gave the oxo-products with the 54% total yield.     

Cage‐like Fe,Na‐Germsesquioxanes: Structure,Magnetism, and Catalytic Activity

A series of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage‐like architectures have a unique type of molecular topology consisting of the hexairon oxo {Fe₆O₁₉} core surrounded in a triangular manner by three cyclic germoxanolates [PhGe(O)O]₅. This structural organization induces antiferromagnetic interactions between the Fe^III ions through the oxygen atoms. Evaluated for this first time in catalysis, these compounds showed a high catalytic activity in the oxidation of alkanes and the oxidative formation of benzamides from alcohols.     

Trifluoromethylchlorosulfonylation of Alkenes: Evidence for an Inner‐Sphere Mechanism by a Copper Phenanthroline Photoredox Catalyst

A visible‐light‐mediated procedure for the unprecedented trifluoromethylchlorosulfonylation of unactivated alkenes is presented. It uses [Cu(dap)₂]Cl as catalyst, and contrasts with [Ru(bpy)₃]Cl₂, [Ir(ppy)₂(dtbbpy)]PF₆, or eosin Y that exclusively give rise to trifluoromethylchlorination of the same alkenes. It is assumed that [Cu(dap)₂]Cl plays a dual role, that is, acting both as an electron transfer reagent as well as coordinating the reactants in the bond forming processes.     

Structure and peculiarities of nanodeformation in Ti–Zr–Ni quasi-crystals

Ti–Zr–Ni samples with a substantial predominance of icosahedral quasicrystalline phase were produced by the melt-spinning technique. Their structure and mechanical properties were studied by X-ray diffraction and nanoindentation methods. The quasicrystalline phase was found to have a primitive lattice with the quasicrystallinity parameter a _q = 0.5200–0.5210?nm. Quasicrystalline deformation behaviour under nanoindentation versus phase composition and structure is discussed in comparison with single crystal W–12?wt%?Ta. The estimated elastic modulus E of the quasicrystalline phase shows no correlation with the element composition. The nanohardness was shown to increase with increasing quasicrystalline-phase perfection. Load–displacement curves of Ti–Zr–Ni quasicrystals (QCs) show stepwise character with alternation of elastic and plastic sections. Such non-uniform plastic flow in QCs might be caused by the localization of plastic deformation in shear bands. The non-uniformity of the plastic deformation increases with the increasing quasicrystalline phase perfection.     

Oxidation of alkanes and alcohols with hydrogen peroxide catalyzed by complex Os3(CO)10(µ‐H)2

Trinuclear carbonyl hydride cluster, Os₃(CO)₁₀(µ‐H)₂, catalyzes oxidation of cyclooctane to cyclooctyl hydroperoxide by hydrogen peroxide in acetonitrile solution. The hydroperoxide partly decomposes in the course of the reaction to afford cyclooctanone and cyclooctanol. Selectivity parameters obtained in oxidations of various linear and branched alkanes as well as kinetic features of the reaction indicated that the alkane oxidation occurs with the participation of hydroxyl radicals. A similar mechanism operates in transformation of benzene into phenol and styrene into benzaldehyde. The system also oxidizes 1‐phenylethanol to acetophenone. The kinetic study led to a conclusion that oxidation of alcohols does not involve hydroxyl radicals as main oxidizing species and apparently proceeds with the participation of osmyl species, ‘Os?O’. Copyright © 2010 John Wiley & Sons, Ltd.     

Regioselective alkane oxygenation with H2O2 catalyzed by titanosilicalite TS-1

Titanosilicalite TS-1 catalyses oxidation of light (methane, ethane, propane and n-butane) and normal higher (hexane, heptane, octane and nonane) alkanes to give the corresponding isomeric alcohols and ketones. The oxidation of higher alkanes proceeds in many cases with a unique regioselectivity. Thus, in the reaction with n-heptane the CH₂ groups in position 3 exhibited a reactivity 2.5 times higher than those of the other methylene groups. This selectivity can be enhanced if hexan-3-ol is added to the reaction mixture, the 3-CH₂/2-CH₂ ratio becoming 10. It is assumed that the unusual selectivity in the oxidation of n-heptane (and other higher alkanes) is due to steric hindrance in the catalyst cavity. As a result, the catalytically active species situated on the catalyst walls can only easily react with certain methylenes of the alkane, which is adsorbed in the cavity taking U-shape (hairpin) conformations.