In situ Fe K-edge X-ray absorption fine structure of a nitrosyl adduct of iron phthalocyanine irreversibly adsorbed on a high area carbon electrode in an acidic electrolyte

Key aspects of the microenvironment surrounding the Fe center in the nitrosyl adduct of iron phthalocyanine, [Fe(Pc)(NO)], have been elucidated from the analysis of the Fe K-edge extended X-ray absorption fine structure (EXAFS) of the material adsorbed on the surface of a high area carbon electrode recorded in situ, in 0.5 M H(2)SO(4). Statistical best fits to the EXAFS data place the Fe center in a five-coordinated square pyramidal configuration shifted away from the Pc plane toward the axially bound NO bent at an angle of ca. 40 degrees with respect to the normal to the Pc plane. This environment is analogous to that of Fe in the nitrosyl adduct of crystalline [Fe(TPP)], where TPP = meso-tetraphenylporphyrinato(2-), determined from X-ray diffraction.     

Diamond and diamond-like carbon from a preceramic polymer

The synthesis of poly(hydridocarbyne), one of a class of carbon-based random network polymers and a structural isomer of polyacetlyene, is reported. The network backbone of this polymer is primarily composed of tetrahedrally hybridized carbon atoms, each bearing one hydride substituent and linked via three carbon-carbon single bonds into a three-dimensional random network of fused rings. This atomic-level carbon network backbone confers unusual properties on the polymer, including facile thermal decomposition to form diamond or diamond-like carbon high-quality films at atmospheric pressure, by direct deposition or by chemical vapor deposition (CVD), without the use of hydrogen or any other reagent.     

Amber‐Woody Scent: Alcohols with Divergent Structure Present Common Olfactory Characteristics and Sharp Enantiomer Differentiation

Only one out of the four possible trans isomers of the important perfumery alcohol Norlimbanol^® ( 1 ) possesses a very strong amber‐woody smell, the isomer 1A with (1′R,3S,6′S) absolute configuration. Its enantiomer 1B is almost odorless and devoid of amber‐woody character, whereas the diastereoisomers 1C and 1D are considerably weaker and perceptible only by the most‐sensitive persons. The same is true for a whole series of perceptual analogs of 1 , including β‐alkoxy alcohols. These ethers belong to two structural classes: [(2,2,6‐trimethylcyclohexyl)oxy]‐ (see 3, 4 , and 16 ) or {[2‐(tert‐butyl)cyclohexyl]oxy}alkan‐2‐ol derivatives (see 19 and 20 ; Table). A superimposition model allowing for good overlap of the respective hydroxylated side chains offers a tentative explanation for the shared perceptual characteristics of the two classes (Fig. 5). The lipophilic cyclohexane moieties present only a minimal overlap in this model, suggesting that quite larger molecules might possess the same smell. (S)‐Configured β‐alkoxy alcohols can conveniently be obtained on a larger scale by enantioselective reduction of the corresponding ketones (Scheme 9).     

Radical para-benzoic acid derivatives: transmission of ferromagnetic interactions through hydrogen bonds at long distances

Investigation of the transmission of magnetic interactions through hydrogen bonds has been carried out for two different benzoic acid derivatives which bear either a tert-butyl nitroxide (NOA) or a poly(chloro)triphenylmethyl (PTMA) radical moiety. In the solid state, both radical acids formed dimer aggregates by the complementary association of two carboxylic groups though hydrogen bonding. This association ensured that atoms with most spin density are separated from one another by more than 15 A. Thus, no competing through-space magnetic exchange interactions are expected in these dimers and, hence, they provide good models to investigate whether noncovalent hydrogen bonds play a role in the long-range transmission of magnetic interactions. The nature of the magnetic exchange interaction and their strengths within similar dimer aggregates in solution was assessed by electron spin resonance (ESR) spectroscopy. In the case of radical NOA, low-temperature ESR experiments showed a weak ferromagnetic interaction between the two radicals in the dimer aggregates (which have the same geometry as in the solid state). In contrast, the corresponding solution ESR study performed with radical PTMA did not lead to any conclusive results, as aggregates were formed by noncovalent interactions other than hydrogen bonds. However, the bulkiness of the poly(chloro)triphenylmethyl radical prevented interdimer contacts in the solid state between regions of high spin density. Hence, solid-state measurements of the alpha phase of PTMA radical provided evidence of the intradimer interaction to confirm the transmission of a weak ferromagnetic interaction through the carboxylic acid bridges, as found for the NOA radical. Moreover, crystallization of the PTMA radical in presence of ethanol to form the beta phase of PTMA radical prevented the dimer formation; this resulted in the suppression of this interaction and provides further evidence of the magnetic exchange mechanism through noncovalent hydrogen bonds at long distances.     

Aggregation and reactivity of the cesium enolate of 6-phenyl-alpha-tetralone: comparison with the lithium enolate

The cesium enolate of 6-phenyl-alpha-tetralone (CsPAT) has a lambda(max) in THF at about 387 nm, but the variation with concentration is too small for application of singular value decomposition. Proton-transfer studies with several indicators show that CsPAT forms monomer-tetramer mixtures with a tetramerization equilibrium constant, K(1,4) = 2.3 x 10(11) M(-3). The pK of the monomer is 23.39 on a scale where fluorene is assigned 22.9 (per hydrogen). For comparison, the lithium enolate, LiPAT, is also a monomer-tetramer with K(1,4) = 4.7 x 10(10) M(-3) and a monomer pK = 14.22. HMPA in large amounts promotes dissociation to monomer with both enolates. Ion-pair S(N)2 initial rates were measured for CsPAT with several alkyl halides and with methyl tosylate and compared with other rates with LiPAT. In all cases, the enolate monomers are much more reactive than the aggregates. Reaction of CsPAT with alkyl halides is generally C-alkylation but HMPA promotes increasing amounts of O-alkylation. A new indicator, 11-methyl-11H-benzo[b]fluorene, has a pK on the cesium scale of 23.39.     

In situ soft X-ray studies of ethylene oxidation mechanisms and intermediates on the Pt(111) surface

In situ studies of ethylene oxidation on Pt(111) have been performed using a powerful combination of fluorescence yield soft X-ray methods for temperatures up to 600 K and oxygen pressures up to 0.01 Torr. Absolute carbon coverages have been determined both in steady-state and dynamic catalytic conditions on the Pt(111) surface. Fluorescence yield near-edge spectroscopy (FYNES) and temperature-programmed fluorescence yield near-edge spectroscopy (TP-FYNES) experiments above the carbon K edge were used to identify the structure and bonding of the dominant surface species during oxidation. TP-FYNES experiments of preadsorbed ethylene coverages in oxygen pressures up to 0.01 Torr indicate a stable intermediate is formed over the 215-300 K temperature range. By comparing the intensity of the C-H sigma resonance at the magic angle with the intensity in the carbon continuum, the stoichiometry of this intermediate has been determined explicitly. Based on calibration with known C-H stoichiometries, the intermediate has a C(2)H(3) stoichiometry for oxygen pressures up to 0.01 Torr, indicating oxydehydrogenation occurs before skeletal oxidation. FYNES spectra at normal and glancing incidences were performed to characterize the structure and bonding of this intermediate. Using FYNES spectra of ethylene, ethylidyne, and acetylene as reference standard, this procedure indicates the oxidation intermediate is tri-sigma vinyl. Thus, oxidation of ethylene proceeds through a vinyl intermediate, with oxydehydrogenation preceding skeletal oxidation.     

Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts

Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions performed in dioxane. The effects of halide and acid impurities on the reactions were also investigated. Recycling experiments on catalysts were carried out in order to evaluate Ti leaching and its effect on activity and selectivity.     

Dynamics of a surface phase transition as monitored by in situ second harmonic generation

The dynamics of the (2 x 2)-3CO <--> dilute phase transition involving CO adsorbed on Pt(111) microfacets has been monitored in situ in a CO-saturated acidic electrolyte using potential step-second harmonic generation techniques. Apparent time constants derived strictly from the optical data were found to be orders of magnitude slower for the forward process as compared to those of the reverse process. This behavior is consistent with the activated nature of CO electrooxidation, which requires the presence of a neighboring adsorbed oxygenated species, for example, hydroxyl, for the process to ensue.