O2 interaction and reactivity on a model hydroxylated rutile(110) surface

Recently several theoretical studies have examined oxygen adsorption on the clean, reduced TiO2(110) surface. However the photocatalytic behavior of TiO2 and the scavenging ability of oxygen are known to be influenced by the presence of surface hydroxyls. In this paper the chemistry of O2 on the hydroxylated TiO2 surface is investigated by means of first-principles total energy calculations and molecular dynamics (MD) simulations. The MD trajectories show a direct, spontaneous reaction between O2 and the surface hydroxyls, thus supporting the experimental hypothesis that the reaction does not necessarily pass through a chemisorbed O2 state. Following this reaction, the most stable chemisorbed intermediates are found to be peroxide species HO2 and H2O2. Although these intermediates are very stable on the short time scale of MD simulations, the energetics suggests that their further transformation is connected to a new 300 K feature observed in the experimental water temperature programmed desorption (TPD) spectrum. The participation of two less stable intermediate states, involving terminal hydroxyls and/or chemisorbed water plus oxygen adatoms, to the desorption process, is not supported by the total energy calculations. Analysis of the projected density of states, however, suggests the possibility that these intermediates have a role in completing the surface oxidation immediately before desorption.     

Reactions of dimethyldivinylsilane,dimethyldivinyltin and allyltrimethyltin with diethylene (tertiary) phosphine)platinum complexes

The compounds [Pt(C₂H₄)₂(PR₃)] [PR₃ = P-tBu₂Me, P(C₆H₁₁)₃, PPh₃] react dimethyldivinylsilane or dimethyldivinyltin to give chelate complexes [Pt{(CH₂CH)₂MMe₂} (PR₃)] (M = Si or Sn). allyltrimethyltin reacts with various diethylene (tertiary phosphine)platinum compounds with cleavage of the allyl group to afford complexes [Pt(SnMe₃)(η³-C₃H₅)(PR₂)]. The NMR spectra (¹³C, ¹H and ³¹P) of the new compounds have been recorded, and the data are discussed in terms of the structures proposed.     

Clustering of chemical databases by means of the projection of maximum overlapping sets similarity measurements onto multidimensional spaces

In this paper, we propose a new method for clustering of chemical databases based on the representation of measurements of structural similarity onto multidimensional spaces. The proposed method permits the tuning of the clustering process through the selection of the dimension of the projection space, the normal vectors and the sensibility of the projection process. The structural similarity of each element regarding to the database elements is projected onto the defined spaces generating clusters that represent the characteristics and diversity of the database and whose size and characteristics can be easily adjusted.     

Excited state enantiodifferentiating interactions between a chiral benzophenone derivative and nucleosides

Time-resolved measurements using nanosecond laser flash photolysis have revealed significant enantiodifferentiation in the interaction between ketoprofen (a chiral benzophenone derivative) and two relevant nucleosides, namely, thymidine and 2'-deoxyguanosine. In both cases, the highest quenching rate constants have been observed for (R)-ketoprofen, the enantiomer with lower pharmacological activity. Photoproduct studies performed in the case of thymidine suggest that the enantiodifferentiating process corresponds to a Paterno-Büchi reaction, leading to the formation of oxetanes. With 2'-deoxyguanosine, the quenching is associated with an electron-transfer process monitored through the generation of a ketyl radical.     

Hexaruthenium carbonyl cluster complexes with basal edge-bridged square pyramidal metallic skeleton: efficient synthesis of 2-imidopyridine derivatives and determination of their reactive sites in carbonyl substitution reactions

The reactions of [Ru(3)(CO)(12)] with half equivalent of 2-amino-6-methylpyridine (H(2)ampy) or 2-aminopyridine (H(2)apy) in refluxing xylene give the hexanuclear products [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-L)(mu-CO)(2)(CO)(14)] (L = ampy, 1; apy, 2). These reactions represent the first high-yield syntheses of hexanuclear complexes with a basal edge-bridged square pyramidal metallic skeleton. Five metal atoms of these complexes are bridged by the N-donor ligand in such a way that the edge-bridging metal atom is attached to the pyridine nitrogen, while the basal atoms of the square pyramid are capped by an imido fragment that arises from the activation of both N-H bonds of the NH(2) group. The reactive sites of these complexes in CO substitution reactions have been determined by studying the reactivity of 1 with triphenylphosphine. Two kinetically controlled monosubstitutions take place on the edge-bridging metal atom in positions cis to the pyridine nitrogen, leading to a mixture of two isomers of formula [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(13)(PPh(3))] (3 and 4). On heating at 80 degrees C, these monosubstituted isomers are transformed, via a dissociative pathway, into the product of thermodynamic control (5), which has the PPh(3) ligand on the apical Ru atom. The di- and trisubstituted derivatives [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(12)(PPh(3))(2)] (6) and [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(11)(PPh(3))(3)] (7) are stepwise formed from 3-5 and PPh(3). Compound 6 has the PPh(3) ligands on the edge-bridging and apical Ru atoms, and compound 7 has an additional PPh(3) ligand on an unbridged basal Ru atom. The compound [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(12)(mu-dppm)] (8), in which a basal and the apical Ru atoms are spanned by the dppm ligand, has been isolated from the reaction of 1 with bis(diphenylphosphino)methane.     

Mass spectrometry of heterocyclic compounds—III. Electron-impact-induced fragmentation of 1,2-benzisothiazole and some 3-substituted derivatives

The mass spectra of fifteen 1,2-benzisothiazoles are reported; their fragmentation patterns have been investigated by labelling experiments, high resolution mass measurements and defocused metastable ion detection. The parent compound of the series, 1,2-benzisothiazole, eliminates HCN after partial inter-ring hydrogen scrambling. The extent of scrambling has been determined for normal daughter ions produced at different electron beam energies and also for metastable daughter ions, and is compared with the data reported for benzothiazole. Some 3-substituted derivatives show unusual fragmentation patterns. The mechanisms of these processes are under further investigation.     

Studies on the synthesis of pentacyclic strychnos indole alkaloids. photocyclization of n-chloroacetyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino[4,3-b]indole derivatives

Photocyclization of 2-chloroacetyl-1,2,3,4,5,6-hexahydro-1, 5-methanoazocino[4,3-b]indole ($\text{5}$) takes place at the indole 4-position to give a 1 ,2 ,3 ,4 , 5 ,6-hexahydro-2 ,11-ethano-1 ,5-methanoazocino [4 , 3-6] indole system. Consequently, the method appears to be unsuitable for constructing the pyrrolidine ring of pentacyclic Strychnos indole alkaloids.     

Pyrylium-containing polymers as sensory materials for the colorimetric sensing of cyanide in water

A sensory polymeric material for the colorimetric sensing of cyanide in water has been developed based on the reactivity of this anion with the pyrylium cation.     

Size evolution of the vibrational predissociation process in Br2...Nen clusters: simulation and kinetic study

A hybrid quantum-classical simulation of the vibrational predissociation of Br2...Nen, (n = 2-11) clusters in the B electronic state is carried out. The time-evolution of the reactants, products, and intermediates is analyzed by a kinetic mechanism consisting of three elementary steps: direct vibrational predissociation (VP), intramolecular vibrational redistribution (IVR), and evaporative cooling (EC). The importance of intramolecular vibrational redistribution followed by evaporative cooling relative to direct vibrational predissociation is shown to increase rapidly with increasing cluster size. Final product state distributions reveal that only one or less Br2 stretching quantum per neon atom is required in order to achieve complete dissociation (n quanta for n < or = 9 and n - 1 for n = 10 and 11). The proportion of available energy going into translation is proposed as a parameter to study the statistical behavior of the Van der Waals clusters. It is shown to depend only on the number of remaining degrees of freedom, a characteristic of a statistical behavior, for n > or = 3.     

Microwave-assisted synthesis of bipyrazolyls and pyrazolyl-substituted pyrimidines

We describe the preparation of 1,4′-bipyrazolyls and 4-pyrazolylpyrimidines by the reaction of 2-pyrazolyl-3-dimethylamino acrylate and acrylonitrile with double nucleophilic reagents such as hydrazines, urea and guanidine. Reactions were performed under microwave irradiation in 5-60 min. This is a useful procedure for the preparation of valuable compounds with applications in medicinal and coordination chemistry.