Classical trajectories and RRKM modeling of collisional excitation and dissociation of benzylammonium and <Emphasis Type="Italic">tert</Emphasis>-butyl benzylammonium ions in a quadrupole-hexapole-quadrupole tandem mass spectrometer

Collision-induced dissociation of the benzylammonium and the 4-tert-butyl benzylammonium ions was studied experimentally in an electrospray ionization quadrupole-hexapole-quadrupole tandem mass spectrometer. Ion fragmentation efficiencies were determined as functions of the kinetic energy of ions and the collider gas (argon) pressure. A theoretical Monte Carlo model of ion collisional excitation, scattering, and decomposition was developed. The model includes simulation of the trajectories of the parent and the product ions flight through the hexapole collision cell, quasiclassical trajectory modeling of collisional activation and scattering of ions, and Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the parent ion decomposition. The results of modeling demonstrate a general agreement between calculations and experiment. Calculated values of ion fragmentation efficiency are sensitive to initial vibrational excitation of ions, scattering of product ions from the collision cell, and distribution of initial ion velocities orthogonal to the axis of the collision cell. Three critical parameters of the model were adjusted to reproduce the experimental data on the dissociation of the benzylammonium ion: reaction enthalpy and initial internal and translational temperatures of the ions. Subsequent application of the model to decomposition of the t-butyl benzylammonium ion required adjustment of the internal ion temperature only. Energy distribution functions obtained in modeling depend on the average numbers of collisions between the ion and the atoms of the collider gas and, in general, have non-Boltzmann shapes.     

Probe molecule chemisorption-low energy ion scattering study of surface active sites present in the orthorhombic Mo-V-(Te-Nb)-O catalysts for propane (amm)oxidation

Methanol and allyl alcohol chemisorption and surface reaction in combination with low energy ion scattering (LEIS) were employed to determine the outermost surface compositions and chemical nature of active surface sites present on the orthorhombic (M1) Mo-V-O and Mo-V-Te-Nb-O phases. These orthorhombic phases exhibited vastly different behavior in propane (amm)oxidation reactions and, therefore, represented highly promising model systems for the study of the surface active sites. The LEIS data for the Mo-V-Te-Nb-O catalyst indicated surface depletion for V (-23%) and Mo (-27%), and enrichments for Nb (+55%) and Te (+165%) with respect to its bulk composition. Only minor changes in the topmost surface composition were observed for this catalyst under the conditions of the LEIS experiments at 400 degrees C, which is a typical temperature employed in these propane transformation reactions. These findings strongly suggested that the bulk orthorhombic Mo-V-Te-Nb-O structure may function as a support for the unique active and selective surface monolayer in propane (amm)oxidation. Moreover, direct evidence was obtained that the topmost surface VO(x) sites in the orthorhombic Mo-V-Te-Nb-O catalyst were preferentially covered by chemisorbed allyloxy species, whereas methanol was a significantly less discriminating probe molecule. The surface TeO(x) and NbO(x) sites on the Mo-V-Te-Nb-O catalyst were unable to chemisorb these probe molecules to the same extent as the VO(x) and MoO(x) sites. Our findings suggested that different surface locations for V(5+) ions in the orthorhombic Mo-V-O and Mo-V-Te-Nb-O catalysts may be primarily responsible for vastly different catalytic behavior exhibited by the Mo-V-O and Mo-V-Te-Nb-O phases. Although the proposed isolated V(5+) pentagonal bipyramidal sites in the orthorhombic Mo-V-O phase may be capable of converting propane to propylene with modest selectivity, the selective 8-electron transformation of propane to acrylic acid and acrylonitrile may require the presence of several surface VO(x) redox sites lining the entrances to the hexagonal and heptagonal channels of the orthorhombic Mo-V-Te-Nb-O phase. The study of allyl alcohol oxidation over the Mo-V-O and Mo-V-Te-Nb-O catalysts further suggested that water plays a critical role during the oxidation of acrolein intermediate to acrylic acid over the orthorhombic (M1 phase) Mo-V-Te-Nb-O catalysts. Finally, the present study strongly indicated that chemical probe chemisorption combined with low energy ion scattering (LEIS) is a novel and highly promising surface characterization technique for the investigation of the active surface sites present in the bulk mixed metal oxides.     

Long‐Range Chemical Ligation from N→N Acyl Migrations in Tryptophan Peptides via Cyclic Transition States of 10‐ to 18‐Members

Chemical ligations to form native peptides from N→N acyl migrations in Trp‐containing peptides via 10‐ to 18‐membered cyclic transition states are described. In this study, a statistical, predictive model that uses an extensive synthetic and computational approach to rationalize the chemical ligation is reported. N→N acyl migrations that form longer native peptides without the use of Cys/Ser/Tyr residues or an auxiliary group at the ligation site were achieved. The feasibility of these traceless chemical ligations is supported by the N?C bond distance in N‐acyl isopeptides. The intramolecular nature of the chemical ligations is justified by using competitive experiments and theoretical calculations.     

Synthesis of highly sterically hindered niobium and tantalum alkoxides and their microhydrolysis in strongly basic medium

We have investigated the interaction of niobium and tantalum alkoxides with pinacol and are reporting here isolation and structural characterization of the products, attractive potential precursors of materials with hierarchical porosity. The general feature in the reactivity of alkoxide complexes with additional ligands is that stabilization of the complexes is achieved due to Brønsted acidity of the ligand and possibility of formation of hydrogen bonds in the structure. Presence of strong organic bases does not influence the complex formation. We were able to isolate, for example, highly moisture-sensitive ortho-pinacolates of Nb and Ta, M(O₂C₆H₁₂)₂(OC₆H₁₂OH), in the presence of excess of triethylamine. The earlier attempts to prepare these complexes were unsuccessful because of extremely high solubility and easy hydrolysis of these species. The first step in microhydrolysis of M(O₂C₆H₁₂)₂(OC₆H₁₂OH), M = Nb, Ta, independently of basicity of the medium provides M₂O(O₂C₆H₁₂)₂(OC₆H₁₂OH)₄, even those highly moisture-sensitive in solution. The general conclusion of this work is that the Lewis acidity and blocking of the coordination sites by bulky alkoxide ligands does not play any important role. The reactivity of the species is not in any way hindered by the complete blocking of the metal centers.     

The Poisson boundary of the mapping class group

A theory of random walks on the mapping class group and its non-elementary subgroups is developed. We prove convergence of sample paths in the Thurston compactification and show that the space of projective measured foliations with the corresponding harmonic measure can be identified with the Poisson boundary of random walks. The methods are based on an analysis of the asymptotic geometry of Teichmüller space and of the contraction properties of the action of the mapping class group on the Thurston boundary. We prove, in particular, that Teichmüller space is roughly isometric to a graph with uniformly bounded vertex degrees. Using our analysis of the mapping class group action on the Thurston boundary we prove that no non-elementary subgroup of the mapping class group can be a lattice in a higher rank semi-simple Lie group. Oblatum 10-V-1995 & 11-IX-1995