Comparison of the bis(ferrocenylethynyl)phenylmethylium cation with bis(ferrocenylethenyl)methylium analogues

Several new ferrocenylethynyl derivatives, (FcCC)₂CHOH, (FcCC)₂CH₂, (FcCC)₂CPhOH have been synthesised from ethynylferrocene. Attempts to synthesise the corresponding bis(ferrocenylethynyl)-stabilised carbocations by hydroxyl or hydride abstraction from the bridging group was unsuccessful for (FcCC)₂CHOH and (FcCC)₂CH₂, respectively. In the case of (FcCC)₂CPhOH, the [(FcCC)₂CPh]⁺ cation could be observed by ¹H and ¹³C NMR, and by UV-Vis-NIR spectroscopy, but was too unstable for isolation or prolonged study in solution. The UV-Vis-NIR spectrum of [(FcCC)₂CPh]⁺ is compared to that of the considerably more stable cations, [Fc(CHCH)₂CH]⁺ and [(FcCHCH)₂CPh]⁺.     

Initial oxidation of brass induced by humidified air

Complementary surface and near-surface analytical techniques have been used to explore a brass (Cu-20Zn) surface before, during, and after exposure in air at 90% relative humidity. Volta potential variations along the unexposed surface are attributed to variations in surface composition and resulted in an accelerated localized growth of ZnO and a retarded more uniform growth of an amorphous Cu₂O-like oxide. After 3 days the duplex oxide has a total mass of 1.3 μg/cm², with improved corrosion protective properties compared to the oxides grown on pure Cu or Zn. A schematic model for the duplex oxide growth on brass is presented.     

Towards the experimental decomposition rate of carbonic acid (H2CO3) in aqueous solution

Dry carbonic acid has recently been shown to be kinetically stable even at room temperature. Addition of water molecules reduces this stability significantly, and the decomposition (H2CO3 + nH2O --> (n+1)H2O + CO2) is extremely accelerated for n = 1, 2, 3. By including two water molecules, a reaction rate that is a factor of 3000 below the experimental one (10 s(-1)) at room temperature was found. In order to further remove the gap between experiment and theory, we increased the number of water molecules involved to 3 and took into consideration different mechanisms for thorough elucidation of the reaction. A mechanism whereby the reaction proceedes via a six-membered transition state turns out to be the most efficient one over the whole examined temperature range. The determined reaction rates approach experimental values in aqueous solution reasonably well; most especially, a significant increase in the rates in comparison to the decomposition reaction with fewer water molecules is found. Further agreement with experiment is found in the kinetic isotope effects (KIE) for the deuterated species. For water-free carbonic acid, the KIE (i.e., kH2CO3/kD2CO3) for the decomposition reaction is predicted to be 220 at 300 K, whereas it amounts to 2.2-3.0 for the investigated mechanisms including three water molecules. This result is therefore reasonably close to the experimental value of 2 (at 300 K). These KIEs are in much better accordance with the experiment than the KIE for decomposition with fewer water entities.     

About the stability of sulfurous acid (H2SO3) and its dimer

The characterization and isolation of sulfurous acid (H2SO3) have never been accomplished and thus still remain one of the greatest open challenges of inorganic chemistry. It is known that H2SO3 is thermodynamically unstable. In this study, however, we show that a Ci-symmetric dimer of sulfurous acid (H2SO3)2 is 3.5 kcal mol-1 more stable than its dissociation products SO2 and H2O at 77 K. Additionally, we have investigated the kinetic stability of the sulfurous acid monomer with respect to dissociation into SO2 and H2O and the kinetic isotope effect (KIE) on this reaction by transition-state theory. At 77 K, the half-life of H2SO3 is 15 x 10(9) years, but for the deuterated molecule (D2SO3) it increases to 7.9 x 10(26) years. At room temperature, the half-life of sulfurous acid is only 24 hours; however, a KIE of 3.2 x 10(4) increases it to a remarkable 90 years. Water is an efficient catalyst for the dissociation reaction since it reduces the reaction barrier tremendously. With the aid of two water molecules, one can observe a change in the reaction mechanism for sulfurous acid decomposition with increasing temperature. The most likely mechanism below 170 K is via an eight-membered transition-state ring; yet, above 170 K, a mechanism with a six-membered transition state ring becomes the predominant one. For deuterated sulfurous acid, this change in reaction mechanism can be observed at 120 K. Consequently, between 120 and 170 K, different predominant reaction mechanisms occur for the decomposition of normal and deuterated sulfurous acid when assisted by two water molecules. However, the much longer half-life of deuterated sulfurous acid and the stability of the sulfurous acid dimer at 77 K are encouraging for future synthesis and characterization under laboratory conditions.     

Reactions of phosphate and phosphorothiolate diesters with nucleophiles: comparison of transition state structures

A series of methyl aryl phosphorothiolate esters (SP) were synthesized and their reactions with pyridine derivatives were compared to those for methyl aryl phosphate esters (OP). Results show that SP esters react with pyridine nucleophiles via a concerted S(N)2(P) mechanism. Br?nsted analysis suggests that reactions of both SP and OP esters proceed via transition states with dissociative character. The overall similarity of the transition state structures supports the use of phosphorothiolates as substrate analogues to probe mechanisms of enzyme-catalyzed phosphoryl transfer reactions.     

A vibrational sum frequency spectroscopy study of the liquid-gas interface of acetic acid-water mixtures: 2. Orientation analysis

Vibrational sum frequency spectroscopy has been used to investigate the surface of aqueous acetic acid solutions. By studying the methyl and carbonyl vibrations with different polarization combinations, an orientation analysis of the acetic acid molecules has been performed in the concentration range 0-100%. The surface tension of acetic acid solutions was also measured in order to obtain the surface concentration. The orientation of the interfacial acetic acid molecules was found to remain essentially constant in an upright position with the methyl group directed toward the gas phase in the whole concentration range. The tilt angle (theta(CH)3) of the symmetry axis of the methyl group with respect to the surface normal was found to be lower than 15 degrees when considering a delta distribution of angles or as narrow as 0 +/- 11 degrees when assuming a Gaussian distribution. Further investigations showed that the C=O bond tilt (theta(C)(=)(O)) of the acetic acid hydrated monomer was constant and close to 55 degrees in the concentration range where it was detected. Finally, the orientation information is discussed in terms of different species of acetic acid, where the formation of a surface layer of acetic acid cyclic dimers is proposed at high acid concentrations.     

The importance of tunneling in the first hydrogenation step in ammonia synthesis over a Ru(0001) surface

The hydrogenation of nitrogen (N(ads)+H(ads)-->NH(ads)) on metal surfaces is an important step in ammonia catalysis. We investigate the reaction dynamics of this hydrogenation step by time independent scattering theory and variational transition state theory (VTST) including tunneling corrections. The potential energy surface is derived by hybrid density functional theory on a model cluster composed of 12 ruthenium atoms resembling a Ru(0001) surface. The scattering calculations are performed on a reduced dimensionality potential energy hypersurface, where two dimensions are treated explicitly and all others are included implicitly by the zero-point correction. The VTST calculations include quantum effects along the reaction coordinate by applying the small curvature tunneling scheme. Even at room temperature (where ruthenium already shows catalytic activity) we find rate enhancement by tunneling by a factor of approximately 70. Inspection of the reaction probabilities shows that the major contribution to reactivity comes from the vibrational ground state of the reactants into vibrationally excited product states. The reaction rates are higher than determined in previous studies, and are compatible with experimental overall rates for ammonia synthesis.     

Raman mapping of a single-layer to double-layer graphene transition

We report on confocal Raman spectroscopy on a few-layer graphene flake. Adjacent single- and double-layer graphene sections allow mapping the transition in vibrational and electronic properties to a second stacked graphene sheet and with it a weak interlayer coupling. Most prominently the width of the D' peak doubles upon going from a single to a double layer, which can be explained within the double-resonant Raman model. The intensities of the G and G' lines decrease at the crossover to a single layer. Contrary to the G' line the G peak position shifts to higher wave numbers, however, not uniformly over the entire section: its frequency fluctuates spatially. The Raman map of the D line intensity shows a non-zero contribution at the boundaries of the flake and the individual sections, which can be attributed either to defects and disorder or to the breakdown of translational symmetry, whereas within the flake no D line signal is detected.