Oxygen atom transfer in models for molybdenum enzymes: isolation and structural, spectroscopic, and computational studies of intermediates in oxygen atom transfer from molybdenum(VI) to phosphorus(III)

Intermediates in the oxygen atom transfer from Mo(VI) to P(III), [Tp(iPr)MoOX(OPR3)] (Tp(iPr) = hydrotris(3-isopropylpyrazol-1-yl)borate; X = Cl-, phenolates, thiolates), have been isolated from the reactions of [Tp(iPr)MoO2X] with phosphines (PEt3, PMePh2, PPh3). The green, diamagnetic oxomolybdenum(IV) complexes possess local C(1) symmetry (by NMR spectroscopy) and exhibit IR bands assigned to nu(Mo==O) (approximately 950 cm(-1)) and nu(P==O) (1140-1083 cm(-1)) vibrations. The X-ray crystal structures of [Tp(iPr)MoOX(OPEt3)] (X = OC6H4-2-sBu, SnBu), [Tp(iPr)MoO(OPh)(OPMePh2)], and [Tp(iPr)MoOCl(OPPh3)] have been determined. The monomeric complexes exhibit distorted octahedral geometries, with coordination spheres composed of tridentate fac-Tp(iPr) and mutually cis monodentate terminal oxo, phosphoryl (phosphine oxide), and monoanionic X ligands. The electronic structures and stabilities of the complexes have been probed by computational methods, with the three-dimensional energy surfaces confirming the existence of a low-energy steric pocket that restricts the conformational freedom of the phosphoryl ligand and inhibits complete oxygen atom transfer. The reactivity of the complexes is also briefly described.     

Characterization of gem-difluoropropargyl synthons through HF loss from protonated molecules in methane chemical ionization mass spectra

Electron impact and methane chemical ionization mass spectra were obtained following gas chromatography/mass spectrometry for several gem-difluoropropargyl compounds, which had been synthesized as potential intermediates for synthesis of gem-difluoromethylene-containing C-3 acetylenes. EI spectra were variable with respect to the presentation of molecular ions, depending on substituent functional groups present. Methane-CI spectra were characterized by loss of 19 mass units from molecular weight with all compounds examined. These [M − 19]⁺ ions often presented as base peaks of the CI spectra, and were more reliably present and abundant than [M + 1]⁺ ions for these compounds. These ions could have been formed by elimination of HF from the protonated molecules under conditions of methane chemical ionization.     

Radical addition reactions: factors determining the transition-state geometry

Interatomic distances in the reaction centers of the addition reactions of (i) H^· to the C=C, C=O, N≡C, and C≡C bonds, (ii) ^·CH₃ radical to the C=C, C=O, and C≡C bonds, and (iii) alkyl, aminyl, and alkoxyl radicals to olefin C=C bonds were determined using a new semiempirical method for calculating transition-state geometries of radical reactions. For all reactions of the type X^· + Y=Z → X— Y—Z^· the r ^# _X...Y distance in the transition state is a linear function of the enthalpy of reaction. Parameters of this dependence were determined for seventeen classes of radical addition reactions. The bond elongation, Δr ^# _X...Y, in the transition state decreases as the triplet repulsion, electronegativity difference between the atoms X and Y in the reaction center, and the force constant of the attacked multiple bond increase. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 894–902, April, 2005.     

Stabilities in field electron emissions from noble‐metal covered W nano‐tips: apex structure dependence

We observed field emission microscopy (FEM) patterns of noble‐metal (NM) covered W nano‐tips with three different apex structures fabricated by field evaporation. Each of the three tips was terminated with a single atom, three atoms or ten atoms. We investigated the temporal changes in the FEM of these tips to discuss the stabilities in the spatial distributions of the field emission (FE) beams. The single‐atom tip showed two characteristics that were superior to the others. First, the beams emitted from the single‐atom tip were the most collimated among the three tips (the semi‐cone angle of 1.0° , FWHM). Second, adsorption of residual gas had little influence on FE from the single‐atom tip, while the other tips were easily contaminated even at ultra high vacuum, resulting in the emission fluctuation. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis and characterization of well-defined poly(methyl methacrylate)/CaCO3/SiO2 three-component composite particles via reverse atom transfer radical polymerization

The attempt to prepare structurally well-defined polymer/inorganic composite particles, i.e., poly(methyl methacrylate) (PMMA)/CaCO₃/SiO₂ three-component composite particles, via reverse atom transfer radical polymerization (ATRP), using 2-2′-azo-bis-isobutyronitrile as initiator and Cu(II) bromide as catalyst was reported. CaCO₃/SiO₂ two-component composite particles were first obtained through sol–gel method, and their morphology and surface element information were determined by transmission electron microscopy and X-ray photoelectron spectroscopy, respectively. The results indicate that the CaCO₃ was encapsulated by the obtained SiO₂. After being modified by silane coupling agent, the CaCO₃/SiO₂ composite particles copolymerized with methyl methacrylate (MMA) under standard reverse ATRP conditions to produce PMMA/CaCO₃/SiO₂ three-component composite particles. In the case concerned, first-order kinetic plots and linear increase of molecular weight (Mn) vs conversion and narrow molecular weight distribution for the graft polymer samples were observed. Furthermore, the gel permeation chromatography results illustrated that both the free PMMA chains from the solvent and the graft PMMA chains from the surface of CaCO₃/SiO₂ two-component composite particles were growing at the same rate. Characterizations of the PMMA-grafted CaCO₃/SiO₂ composite particles were done by Fourier transform infrared and thermogravimetric analysis. The results showed that the surface of the modified inorganic particles was grafted by the MMA and that the grafting percentage was about 8.7%.     

Atom transfer radical homo‐ and block copolymerization of methyl 1‐bicyclobutanecarboxylate

A non‐olefinic monomer, methyl 1‐bicyclobutanecarboxylate (MBC), was successfully polymerized by the controlled/“living” atom transfer radical polymerization (ATRP) technique, resulting in a well‐defined homopolymer, PMBC, with only cyclobutane ring units in the polymer chain. An AB block copolymer poly(methyl 1‐bicyclobutanecarboxylate)‐b‐polystyrene (PMBC‐b‐PS), having an all‐ring unit segment, was also synthesized with narrow polydispersity and designed number‐average molecular weight in addition to precise end groups. The ¹H NMR spectra, glass‐transition temperature, and thermal stability of PMBC, PMBC‐b‐PS, and PS‐b‐PMBC were investigated. The experimental results showed that the cyclobutane rings in the two block polymers improved their thermal stability. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1929–1936, 2002     

GRECP/MRD‐CI calculations on the Hg atom and HgH molecule

Multireference single‐ and double‐excitation configuration interaction (MRD‐CI) calculations of transition energies for the Hg atom and spectroscopic constants for the HgH molecule are carried out with the generalized relativistic effective core potential (GRECP) method. A new selection criterium for the reference configurations is discussed. The calculated spectroscopic constants are compared with experimental data and results of calculations of other groups. Improvement of accuracy is mainly observed for bond lengths from the GRECP/MRD‐CI calculations (without applying the T = 0 correction) with respect to the results of other groups. Analysis of the quality of the approximations employed is carried out. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

On the 6-exo-trig ring closure of substituted 5-hexen-1-oxyl radicals

Substituted 5-hexen-1-oxyl radicals have been generated from N-(5-hexen-1-oxy)-5-(p-methoxyphenyl)-4-methylthiazole-2(3H)-thiones under tin-free conditions and have been successfully applied as reactive intermediates in a mechanistic study on the formation of bromomethyl-substituted tetrahydropyrans via 6-exo-trig selective cyclizations.     

溶剂化金属原子浸渍法制备Pd-Cu/γ-Al2O3低温CO氧化催化剂

Nano-particle Pd/γ-Al₂O₃ monometallic and Pd-Cu/γ-Al₂O₃ bimetallic catalysts were prepared by solvated metal atom impregnation (SMAI) method. The results of XRD measurement indicated that Pd- Cu alloy was formed in the bimetallic catalysts and the crystalline particle size of the alloy increased as Cu contents increased with av-erage diameters < 6.0nm for all the samples. XPS and Auger spectra showed that Pd was in zero- valent state, Cu existed mainly in zero- valent state and partially in monovalent state Cu⁺. The Pd/γ-Al₂O₃ and Pd-Cu/γ-Al₂O₃ catalysts exhibited higher activity for CO oxidation at low temperature. The activity of Pd-Cu/γ-Al₂O₃ bimetallic catalyst was higher than that of Pd/γ-Al₂O₃ monometallic catalyst. The Pd-Cu/γ-Al₂O₃ catalyst with Pd/Cu atomic ratio of 1∶1 showed the highest activity.