Ion-molecule reactions involving methyl isocyanide and methyl cyanide

Ion-molecule reactions involving methyl isocyanide and methyl cyanide have been performed in a new rf-only hexapole collision cell inserted in a large-scale tandem mass spectrometer. Beside protonation processes, N-methyl cyanogen ions (CH(3)N(+)CCN) and 1-methyleneiminium-1- ethylenium ions (CH(2)CN(+)CH(2)) have been produced in high yield and fully characterized by high-energy collisional activation. The unimolecular chemistry of the molecular ions of caffeine (1,3,7-trimethyl xanthine) has been revisited on the basis of these new results.     

Solution and crystal conformations of myrionine, a new 8beta-alkyl-cis-decahydroquinoline of Myrioneuron nutans

Myrionine (1), a new 8beta-alkyl-cis-decahydroquinoline, was isolated from Myrioneuron nutans. Its structure was determined by spectral methods and then confirmed by X-ray analysis and total synthesis. In solution, 1 gives rise to an N-in/N-out equilibrium. The solvent has weak influence on the N-in/N-out ratio for myrionine (1), whereas together with the anions, it plays an important role for myrionine hydrochloride (9) and hydroiodide (10). The two N-in and N-out conformations obtained separately by crystallization of 9 and 10, respectively, were analyzed by X-ray diffraction.     

Contact angle of water on polystyrene thin films: effects of CO(2) environment and film thickness

We examine the contact angle of water droplets on polystyrene (PS) thin films of varying thicknesses supported by silicon wafers under both air and pressurized carbon dioxide (CO2) environments. At 23 degrees C, the contact angle is found to increase upon increasing CO2 pressure in the vapor regime and then levels off in the liquid CO2 regime. A macroscopic model based on Young's equation and the geometric-mean method for interfacial tensions, and long-range van der Waals interactions, correctly predicts the trends and the magnitude of the contact angle dependence on pressure, although deviations occur at high CO2 activities. The contact angle was also found to depend on film thickness, h, when h was comparable to or smaller than 50 nm. Specifically, the contact angle decreases with decreasing PS film thickness. This behavior could be accounted for with the use of a model that incorporates the effects of film thickness, CO2 pressure, and the long-range van der Waals potential.     

Heats of formation of diphosphene, phosphinophosphinidene, diphosphine, and their methyl derivatives, and mechanism of the borane-assisted hydrogen release

The heats of formation of diphosphene (cis- and trans-P2H2), phopshinophosphinidene (singlet and triplet H2PP) and diphosphine (P2H4), as well as those of the P2H and P2H3 radicals resulting from PH bond cleavages, have been calculated by using high-level ab initio electronic structure theory. Energies were calculated using coupled-cluster theory with a perturbative treatment for triple excitations (CCSD(T)) and employing augmented correlation consistent basis sets with additional tight d-functions on P (aug-cc-pV(n+d)Z) up to quadruple- or quintuple-zeta, to perform a complete basis set extrapolation for the energy. Geometries and vibrational frequencies were determined with the CCSD(T) method. Core-valence and scalar relativistic corrections were included, as well as scaled zero-point energies. We find the following heats of formation (kcal/mol) at 298 [0] K: DeltaH(degree)(f)(P2H) = 53.4 [54.4]; DeltaH(degree)(f)(cis-P2H2) = 32.0 [33.9]; DeltaH(degree)(f)(trans-P2H2) = 28.7 [30.6]; DeltaH(degree)(f)(H2PP) = 53.7 [55.6]; DeltaH(degree)(f)(3H2PP) = 56.5 [58.3]; DeltaH(degree)(f)(P2H3) = 32.3 [34.8]; DeltaH(degree)(f)(P2H4) = 5.7 [9.1] (expt, 5.0 +/- 1.0 at 298 K); and DeltaH(degree)(f)(CH3PH2) = -5.0 [-1.4]. We estimate these values to have an accuracy of +/-1.0 kcal/mol. In contrast to earlier results, we found a singlet ground state for phosphinophosphinidene (H2PP) with a singlet-triplet energy gap of 2.8 kcal/mol. We calculated the heats of formation of the methylated derivatives CH3PPH, CH3HPPH2, CH3PPCH3, CH3HPP, (CH3)2PP, (CH3)2PPH2, and CH3HPPHCH3 by using isodesmic reactions at the MP2/CBS level. The calculated results for the hydrogenation reactions RPPR + H2 --> RHPPHR and R2PP + H2 --> R2PPH2 show that substitution of an organic substituent for H improves the energetics, suggesting that secondary diphosphines and diphosphenes are potential candidates for use in a chemical hydrogen storage system. A comparison with the nitrogen analogues is given. The mechanism for H2-generation from diphosphine without and with BH3 as a catalyst was examined. Including tunneling corrections, the rate constant for the catalyzed reaction is 4.5 x 1015 times faster than the uncatalyzed result starting from separated catalyst and PH2PH2.     

Computational study of the release of H2 from ammonia borane dimer (BH3NH3)2 and its ion pair isomers

High-level electronic structure calculations have been used to map out the relevant portions of the potential energy surfaces for the release of H2 from dimers of ammonia borane, BH3NH3 (AB). Using the correlation-consistent aug-cc-pVTZ basis set at the second-order perturbation MP2 level, geometries of stationary points were optimized. Relative energies were computed at these points using coupled-cluster CCSD(T) theory with the correlation-consistent basis sets at least up to the aug-cc-pVTZ level and in some cases extrapolated to the complete basis set limit. The results show that there are a number of possible dimers involving different types of hydrogen-bonded interactions. The most stable gaseous phase (AB)2 dimer results from a head-to-tail cyclic conformation and is stabilized by 14.0 kcal/mol with respect to two AB monomers. (AB)2 can generate one or two H2 molecules via several direct pathways with energy barriers ranging from 44 to 50 kcal/mol. The diammoniate of diborane ion pair isomer, [BH4-][NH3BH2NH3+] (DADB), is 10.6 kcal/mol less stable than (AB)2 and can be formed from two AB monomers by overcoming an energy barrier of approximately 26 kcal/mol. DADB can also be generated from successive additions of two NH3 molecules to B2H6 and from condensation of AB with separated BH3 and NH3 molecules. The pathway for H2 elimination from DADB is characterized by a smaller energy barrier of 20.1 kcal/mol. The alternative ion pair [NH4+][BH3NH2BH3-] is calculated to be 16.4 kcal/mol above (AB)2 and undergoes H2 release with an energy barrier of 17.7 kcal/mol. H2 elimination from both ion pair isomers yields the chain BH3NH2BH2NH3 as product. Our results suggest that the neutral dimer will play a minor role in the release of H2 from ammonia borane, with a dominant role from the ion pairs as observed experimentally in ionic liquids and the solid state.     

The key role of the latent N–H group in Milstein's catalyst for ester hydrogenation

We previously demonstrated that Milstein''s seminal diethylamino-substituted PNN-pincer–ruthenium catalyst for ester hydrogenation is activated by dehydroalkylation of the pincer ligand, releasing ethane and eventually forming an NHEt-substituted derivative that we proposed is the active catalyst. In this paper, we present a computational and experimental mechanistic study supporting this hypothesis. Our DFT analysis shows that the minimum-energy pathways for hydrogen activation, ester hydrogenolysis, and aldehyde hydrogenation rely on the key involvement of the nascent N–H group. We have isolated and crystallographically characterized two catalytic intermediates, a ruthenium dihydride and a ruthenium hydridoalkoxide, the latter of which is the catalyst resting state. A detailed kinetic study shows that catalytic ester hydrogenation is first-order in ruthenium and hydrogen, shows saturation behavior in ester, and is inhibited by the product alcohol. A global fit of the kinetic data to a simplified model incorporating the hydridoalkoxide and dihydride intermediates and three kinetically relevant transition states showed excellent agreement with the results from DFT.

We report a detailed mechanistic study of ester hydrogenation catalyzed by the activated form of Milstein’s catalyst. Catalyst activation leads to the replacement of a dialkylamino side group with an NHEt group, which has a key role in catalysis.     

Synthese und Struktur von Mo2NCl8 und Mo3N2Cl11

Synthesis and Crystal Structure of Mo_2<>NCl₈ and Mo₃N₂Cl₁₁ The reaction of MoCl₅ with Cl₃VNCl at 140 °C in a sealed glass ampoule yields air sensitive black crystals of the mixed valent molybdenum(V, VI) nitride chloride, Mo₂NCl₈. It crystallizes in the monoclinic space group P2/c with a = 996.1(1), b = 629.4(1), c = 1780.8(3) pm, β = 101.82(2)°, and Z = 4. The crystal structure consists of dinuclear C₂‐symmetrical units [Cl₂(N≡)Mo(μ₂‐Cl)₃Mo(≡N)Cl₂]^— and [Cl₄Mo(μ₂‐Cl)MoCl₄]⁺, connected in an alternating sequence by asymmetric nitrido bridges Mo≡N‐Mo to form chains. The reaction of Cl₃VNCl with MoCl₃ at 140 °C affords Mo₃N₂Cl₁₁, but for the prolonged reaction period, MoNCl₃ is observed in addition. Mo₃N₂Cl₁₁ can also be obtained from MoNCl₃ and MoCl₅ (2:1) at 140 °C. It forms orthorhombic, black crystals with the space group Pca2₁ and a = 1256.1(1), b = 1001.9(1), c = 1330.10(5) pm, and Z = 4. The structure contains the same dinuclear units [Cl₂(N≡)Mo(μ₂‐Cl)₃Mo(≡N)Cl₂]^— as in Mo₂NCl₈, which in this case are connected with MoCl₄⁺ moieties by asymmetric nitrido bridges Mo≡N‐Mo forming chains. In Mo₂NCl₈ the Mo‐N distances in the nearly linear nitrido bridges are 167.6(2), and 214.8(2) pm, whereas in case of Mo₃N₂Cl₁₁ two sets of Mo‐N distances of 166, 8(4) and 214, 0(4) pm as well as 166, 9(4) and 211, 9(4) pm are observed.     

Dilute acid hydrolysis of softwoods

Whole tree chips obtained from softwood forest thinnings were converted to ethanol via a two-stage dilute acid hydrolysis followed by yeast fermentation. The chips were first impregnated with dilute sulfuric acid, then pretreated in a steam explosion reactor to hydrolyze, more than 90% of the hemicellulose and approx 10% of the cellulose. The hydrolysate was filtered and washed with water to recover the sugars. The washed fibers were then subjected to a second acid im pregnation and hydrolysis to hydrolyze as much as 45% of the reamining cellulose. The liquors from both hydrolysates were combined and fermented to ethanol by a Saccharomyces cerevisiae yeast that had been adapted to the inhibitors. Based on available hexose sugars, ethanol yields varied from 74 to 89% of theoretical. Oligosaccharide contents higher than about 10% of the total available sugar appear to have a negative impact on ethanol yield.     

to -12pt [-12pt]to 16ptRapid Note Wavefunctions for the Luttinger liquid

Standard bosonization techniques lead to phonon-like excitations in a Luttinger liquid (LL), reflecting the absence of Landau quasiparticles in these systems. Yet in addition to the above excitations some LL are known to possess solitonic states carrying fractional quantum numbers (e.g. the spin 1/2 Heisenberg chain). We have reconsidered the zero modes in the low-energy spectrum of the Gaussian boson LL Hamiltonian both for fermionic and bosonic LL: in the spinless case we find that two elementary excitations carrying fractional quantum numbers allow to generate all the charge and current excited states of the LL. We explicitly compute the wavefunctions of these two objects and show that one of them can be identified with the 1D version of the Laughlin quasiparticle introduced in the context of the Fractional Quantum Hall effect. For bosons, the other quasiparticle corresponds to a spinon excitation. The eigenfunctions of Wen's chiral LL Hamiltonian are also derived: they are quite simply the one dimensional restrictions of the 2D bulk Laughlin wavefunctions. Received 26 January 1999 and Received in final form 21 April 1999     

Application of the Mass Spectrometry for Determining Lead Isotopic Composition in Galena Samples of Vietnam

Lead isotopic composition of galena in lead- zine deposits play an important role in determining their age and genesis.