Hyperaromatic stabilization of arenium ions: a remarkable cis stereoselectivity of nucleophilic trapping of β-hydroxyarenium ions by water

Cis- and trans-1,2-dihydrodiol isomers of benzene undergo acid-catalyzed dehydration to form phenol. In principle the isomeric substrates react through a common β-hydroxybenzenium (cyclohexadienyl) carbocation. Notwithstanding, the isomers show a large difference in reactivity, k(cis)/k(trans) = 4500. This difference is reduced to k(cis)/k(trans) = 440 and 50 for the 1,2-dihydrodiols of naphthalene and 9,10-dihydrodiols of phenanthrene, respectively, and to 6.9 for the dihydrodiols of the nonaromatic 7,8-double bond of acenaphthylene. Because the difference in stabilities of cis- and trans-dihydrodiols should be no more than 2-3-fold, these results imply a high cis stereoselectivity for nucleophilic trapping of a β-hydroxyarenium cation by water in the reverse of the carbocation-forming reaction. This is confirmed by studies of the 10-hydroxy-9-phenanthrenium ion generated from aqueous solvolyses of the trans-9,10-bromohydrin derivative of phenanthrene and the monotrichloroacetate ester of the phenanthrene cis-9,10-dihydrodiol. The cis stereoselectivity of forward and reverse reactions is explained by the formation (in the "forward" reaction) of different conformations of carbocation from cis- and trans-dihydrodiol reactants with respectively β-C-H and β-C-OH bonds in pseudoaxial positions with respect to the charge center of the carbocation optimal for hyperconjugation. Formation of different conformations is constrained by departure of the (protonated) OH leaving group from a pseudoaxial position. The difference in stability of the carbocations is suggested to stem (a) from the greater hyperconjugative ability of a C-H than a C-OH bond and (b) from enhanced conjugation arising from the stabilizing influence of an aromatic ring in the no-bond resonance structures representing the hyperconjugation (C(6)H(6)OH(+) ? C(6)H(5)OH H(+)). This is consistent with an earlier suggestion by Mulliken and a demonstration by Schleyer that the benzenium ion is subject to hyperconjugative aromatic stabilization. It is proposed that, in analogy with the terms homoconjugation and homoaromaticity, arenium ions should be considered as "hyperaromatic".     

Extending the range of neutral N-donor ligands available for metal catalysts: N-[1-alkylpyridin-4(1H)-ylidene]amides in palladium-catalyzed cross-coupling reactions

N-[1-Alkylpyridin-4(1H)-ylidene]amides (PYAs) are a new class of easily prepared, neutral N-donor ligands that share some features in common with N-heterocyclic carbenes. They are strongly electron-donating toward metal centers, and a palladium(II) complex of one of these ligands has been shown to successfully catalyze both the Heck-Mizoroki and Suzuki-Miyaura cross-coupling reactions.     

Acid-catalyzed dehydration of naphthalene-cis-1,2-dihydrodiols: origin of impaired resonance effect of 3-substituents

Acid-catalyzed dehydrations of substituted naphthalene-cis-1,2-dihydrodiols occur with loss of the 1- or 2-OH group to form 2- and 1-naphthols, respectively. Effects of substituents MeO, Me, H, F, Br, I, and CN at 3-, 6-, and 7-positions of the naphthalene ring are consistent with rate-determining formation of β-hydroxynaphthalenium ion (carbocation) intermediates. For reaction of the 1-hydroxyl group the 3-substituents are correlated by the Yukawa-Tsuno relationship with ρ = -4.7 and r = 0.25 or by σ(p) constants with ρ = -4.25; for reaction of the 2-hydroxyl group the 3-substituents are correlated by σ(m) constants with ρ = -8.1. The correlations for the 1-hydroxyl imply a surprisingly weak resonance interaction of +M substituents (MeO, Me) with a carbocation reaction center but are consistent with the corresponding correlation for acid-catalyzed dehydration of 3-substituted benzene-cis-1,2-dihydrodiols for which ρ = -6.9 and r = 0.43. Substituents at the 6- and 7-positions of the naphthalene rings by contrast are correlated by σ(+) with ρ = -3.2 for reaction of the 1-hydroxyl group and ρ = -2.7 for reaction of the 2-hydroxyl group. The unimpaired resonance implied by these substituent effects appears to be inconsistent with a previous explanation of the weak resonance of the 3-substituents in terms of imbalance of charge development and/or nonplanarity of the benzenium ring in the transition state. An alternative possibility is that the adjacent hydroxyl group interferes sterically with conjugation of +M substituents. "Hyperaromaticity" of the arenium ion intermediates does not appear to be a factor influencing this behavior.     

A versatile and modular approach to functionalisation of deep-cavity cavitands via"click" chemistry

The surface modification of deep-cavity cavitands has been demonstrated by using the azide-alkyne "click" coupling to attach dendritic macromolecules or linear polymers onto their periphery. The resulting set of macromolecular cavitands exhibited tuneable solubility yet retained the ability to encapsulate guest molecules.     

Transfer of lipid and phase reorganisation in self-assembled liquid crystal nanostructured particles based on phytantriol

The internal structure of dispersed liquid crystal nanostructured particles of the V(2) and H(2) phases, termed cubosomes and hexosomes respectively, is integral to their application in the pharmaceutical, agricultural and food industries. However the nanostructure is susceptible to change upon incorporation of other lipids and hence it is important to understand the potential for interparticle lipid transfer for such particles when they encounter a particle of dissimilar lipid content. Using time resolved synchrotron small angle X-ray scattering, we have investigated the transfer of material between cubosomes composed of phytantriol with three different particle types of dissimilar composition, (i) hexosomes and (ii) emulsified microemulsion composed of phytantriol and vitamin E acetate, and (iii) cubosomes prepared from glycerol monooleate. It was found that material was transferred between the different dispersed nanostructured particles, with the transfer being caused by compositional ripening. Somewhat counter-intuitively the transfer was bidirectional with phytantriol being more rapidly transferred than the minor component vitamin E acetate. The greater lipophilicity of vitamin E acetate supports previous studies suggesting greater mobility for the less lipophilic components, regardless of the more efficient transfer route to achieve uniform composition. When particles comprising lipids with similar lipophilicities were mixed, the transfer was limited and did not achieve completion; a phase change between cubic nanostructures required to achieve complete mixing provides an apparent barrier to further compositional ripening. The conclusions from this study provide additional support to lipid transfer mechanisms, and highlight some subtleties in using dissimilar lipid mixtures in e.g. food applications.     

Cross section measurements of the Pd(p, γ)Ag, Sn(p, γ)Sb, and Sn(α, γ)Te reactions relevant to the astrophysical rp- and γ-processes

Total cross section measurements for the ¹⁰²Pd(p, γ)¹⁰³Ag and ¹¹⁶Sn(p, γ)¹¹⁷Sb reactions have been performed in the proton energy range 2.6 to 4.25 MeV, and for the ¹¹²Sn(α, γ)¹¹⁶Te reaction over the alpha beam energy range 7.0 to 10.5 MeV. An activation technique was used in which gamma rays from decays of the reaction products were detected off-line by two hyper-pure germanium detectors in a low background environment. Where possible, reaction rates are derived and the results compared to those of calculations generated by the NON-SMOKER and the MOST statistical model codes so as to judge their applicability for describing the cross sections needed for network calculations of nucleosynthesis in explosive astrophysical environments via the γ- and rp-processes.     

Large-area In2O3 ordered pore arrays and their photoluminescence properties

Large-area In₂O₃ ordered pore arrays were prepared on glass and silicon substrates by the sol–gel technique based on colloidal monolayer spheres. The morphologies of such arrays are determined by precursor concentration used and colloidal sphere size, and are thus controllable. It has been shown that the formed ordered pore arrays consist of In₂O₃ polycrystallites. The photoluminescence measurement of the In₂O₃ ordered pore arrays shows that there is a strong photoluminescence band in the blue-green region centered around 465 nm, which does not exist in the bulk materials. Further experiments reveal that this peak originates from the oxygen deficiencies in In₂O₃ skeletons. This polydomain ordered pore-structured array could be of great potential for Si-based integrated nanophotonics and optoelectronic devices of the next generation, in addition to new gas sensors. PACS  01.30.-y; 78.20.-e; 78.55.-m; 78.55.Et     

Detection of impurity segregation in zone-confined, polycrystalline tin-doped indium oxide thin films by STM and AFM

This paper discusses the possibility of using STM and AFM to image the dopant material in a segregated state. Samples of tin-doped indium oxide were prepared using a zone-confining process. The resultant material has dopant species segregated over certain grain boundaries at desired positions while the others remain dopant free. Samples were then imaged using STM, AFM and STEM. Enhanced contrast from the dopant rich grain boundaries and a larger grain size are observed at the surface making an interface with the substrate as compared to the free surface of the sample, while secondary electron STEM images show these grains to be smaller in size and the boundaries to be almost physically flat. This is interpreted to be a consequence of the zone-confining effect.     

Delayed predissociation and collision-induced processes of the ammonia di-cation NH32+

Reactions of NH₃²⁺ di-cations, observed a few microseconds after formation by electron ionisation of ammonia, have been studied in a double-focusing mass spectrometer using techniques of ion translational energy spectroscopy. Fragmentation reactions occuring under unimolecular conditions correspond to predissociation processes, but lack of knowledge about states of NH₃²⁺ precludes any definitive interpretation. A partial tentative interpretation, using arguments by analogy with isoelectronic neutral species, is proposed. Almost all collision-induced fragmentations required electron transfer forming NH₃⁺ as an intermediate step, so the non-dissociative electron transfer processes were also studied. The most unexpected collision-induced fragmentation reaction was that which formed H₃⁺ fragment ions.