The mechanisms of the reactions of W and W+ with COx (x=1, 2): a computational study

The mechanisms of the reactions of W and W+ with COx (x=1, 2) were studied at the CCSD(T)/[SDD+6-311G(d)]//B3LYP/[SDD+6-31G(d)] level of theory. It was shown that the gas-phase reaction of W with CO2 proceeds with a negligible barrier via an insertion pathway, W(7S)+CO2(1A1)-->W(eta2-OCO)(6A')-->OW(eta1-CO)(1A)-->WO (3Sigma+)+CO(1Sigma). This oxidation process is calculated to be exothermic by 32.4 kcal/mol. Possible intermediates of this reaction are the W(eta2-OCO) and OWCO complexes, among which the latter is 37.4 kcal/mol more stable and lies 39.7 and 7.3 kcal/mol lower than the reactants, W(7S)+CO2(1A1), and the products, WO (3Sigma+)+CO(1Sigma), respectively. The barrier separating W(eta2-OCO) from OWCO is 8.0 kcal/mol (relative to the W(eta2-OCO) complex), which may be characterized as a W+delta-(CO2)-delta charge-transfer complex. Ionization of W does not change the character of the reaction of W with CO2: the reaction of W+ with CO2, like its neutral analog, proceeds via an insertion pathway and leads to oxidation of the W-center. The overall reaction W+(6D) + CO2(1A1)-->W(eta1-OCO)+(6A)-->OW(eta1-CO)+(4A)-->WO+(4Sigma+)+CO(1Sigma) is calculated to be exothermic by 25.4 kcal/mol. The cationic reaction proceeds with a somewhat large (9.9 kcal/mol) barrier and produces two intermediates, W(eta1-OCO)+(6A) and OW(eta1-CO)+(4A). Intermediate W(eta1-OCO)+(6A) is 20.0 kcal/mol less stable than OW(eta1-CO)+(4A), and separated from the latter by a 35.2 kcal/mol barrier. Complex W(eta1-OCO)+(6A) is characterized as an ion-molecular complex type of W+-(CO2). Gas-phase reactions of M=W/W+ with CO lead to the formation of a W-carbonyl complex M(eta1-CO) for both M=W and W+. The C-O insertion product, OMC, lies by 5.2 and 69.3 kcal/mol higher than the corresponding M(eta1-CO) isomer, for M=W and W+, respectively, and is separated from the latter by a large energy barrier.     

KA-14 Lidar for Emission Spectra of Crude Oil from the Absheron Peninsula

Russian Physics Journal - The paper deals with the use of the light detection and ranging (Lidar) system KA-14 for fluorescence spectra of crude oil spillage on the Caspian Sea and the Absheron...     

Revisiting the polyoxometalate-based late-transition-metal-oxo complexes: the "oxo wall" stands

Terminal oxo complexes of the late transition metals Pt, Pd, and Au have been reported by us in Science and Journal of the American Chemical Society. Despite thoroughness in characterizing these complexes (multiple independent structural methods and up to 17 analytical methods in one case), we have continued to study these structures. Initial work on these systems was motivated by structural data from X-ray crystallography and neutron diffraction and (17)O and (31)P NMR signatures which all indicated differences from all previously published compounds. With significant new data, we now revisit these studies. New X-ray crystal structures of previously reported complexes K(14)[P(2)W(19)O(69)(OH(2))] and "K(10)Na(3)[Pd(IV)(O)(OH)WO(OH(2))(PW(9)O(34))(2)]" and a closer examination of these structures are provided. Also presented are the (17)O NMR spectrum of an (17)O-enriched sample of [PW(11)O(39)](7-) and a careful combined (31)P NMR-titration study of the previously reported "K(7)H(2)[Au(O)(OH(2))P(2)W(20)O(70)(OH(2))(2)]." These and considerable other data collectively indicate that previously assigned terminal Pt-oxo and Au-oxo complexes are in fact cocrystals of the all-tungsten structural analogues with noble metal cations, while the Pd-oxo complex is a disordered Pd(II)-substituted polyoxometalate. The neutron diffraction data have been re-analyzed, and new refinements are fully consistent with the all-tungsten formulations of the Pt-oxo and Au-oxo polyoxometalate species.     

Chemisorption on a quantum-well wire

The specific features of chemisorption on a quantum-well wire are studied. It is shown that the energy of an electron of an adatom chemisorbed on the quantum-well wire changes jumpwise with variations in the wire radius.     

Structural studies and T c dependence in La2−x Dy x Ca y Ba2Cu4+y O z type mixed oxide superconductors

A new series of mixed oxide superconductors with the stoichiometric composition La_2−x Dy _x Ca _y Ba₂Cu_4+y O _z (x=0.0 − 0.5, y=2x) has been studied for structural and superconductiong properties. Our earlier studies on La_2−x (Y/Er) _x Ca _y Ba₂Cu_4+y O _z series, show a strong dependence of T _c on hole concentration (p _sh). In the present work, the results of the analysis of the neutron diffraction measurements at room temprerature on x=0.3 and 0.5 samples are reported. It is interesting to know that Ca substitutes for both La and Ba site with concomitant displacement of La onto Ba site. Superconductivity studies show that maximum T _c is obtained for x=0.5, y=1.0 sample (T _c ∼ 75 K), for La_1.5Dy_0.5Ca₁Ba₂Cu₅O _z (La-2125).     

Preparation and physicochemical properties of polymeric complexes of methyl benzimidazol-2-ylcarbamate with apple pectin

Polymeric complexes have been obtained by the combined mechanical treatment of enzyme-treated apple pectin and methyl benzimidazol-2 -ylcarbamate, and their physicochemical properties have been studied.Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 896–900, November-December, 1995. Original article submitted May 11, 1995.