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11.
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Ab initio calculations have been performed at the self-consistent field (HF) level, and its perturbative extensions up to fourth-order (MPn), for several electronic states of nitroxylium (NO) as well as for a large number of reference species. Geometries are optimized at the HF/DZ and HF/DZP levels (double zeta and double zeta plus polarization bases). The ground state is found to be the D3h 1A1′ state, with the C2v 1A1 (closed Y) state higher by 0.94 eV. The relationship between adding electrons or oxygen atoms to NO+ and NO is explored, especially in relation to fragmentation energies of NO (q = 0 or 1). A comparison is drawn between NO and two isoelectronic species, CO3 and C(CH2)3, where no surprises are found. 相似文献
13.
Influence of Lattice Defects of Graphite on the Formation of Graphite Hydrogensulfate Various natural and synthetic graphites were oxidized with chromic acid in sulfuric acid to the 1st stage of graphite hydrogensulfate with the intent of determining the inhibition of intercalation by lattice defects. More oxidant than required by stoichiometry is consumed because slow total oxidation to CO2 is superimposed even at room temperature. The activation energy for total oxidation is reduced by lattice defects. With some graphites, separation of the intercalation reaction from total oxidation was accomplished using calorimetry. The reaction enthalpy in the oxidation of well-crystallized graphites to the graphite salt is ?3.05 kJ/mol C. 相似文献
14.
Zusammenfassung Am Beispiel des Aerosils wurde die Ver?nderung der Oberfl?che des Siliciumdioxids bei der Entwicklung verschiedener hydrolytischer
Agentien untersucht. Die Oberfl?che des Aerosils enthielt ursprünglich neben Silanolgruppen in erheblichem Umfang Siloxangruppen.
Mit kaltem Wasser, mit ammoniakalischer Brenzkatechin-L?sung und bei kürzerer Einwirkung von siedendem Wasser wurde eine teilweise
Hydrolyse der Siloxan-Bindungen erreicht, doch, wurden nie mehr als 3.3 Silanolgruppen pro 100 ?2 erhalten.
Nach l?ngerer Einwirkung von siedendem Wasser wurde eine Abnahme der spez. Oberfl?che und der Zahl der Silanolgruppen pro
Fl?cheneinheit beobachtet. Im Elektronenmikroskop zeigten die Teilchen dieser Aerosile Hüllen geringerer Dichte aus feinporigem
Siliciumdioxid. Infolge der extrem engen Poren wurde ein erheblicher Teil der Oberfl?che und der Silanolgruppen bei den Messungen
nicht erfa?t. Konz. Ammoniak und in geringerem Ma?e auch lange Lagerung an der Atmosph?re hatten ?hnliche Wirkung.
überhitzter Wasserdampf katalysierte bei 200° die Abspaltung von Wasser aus Silanolgruppen. Die Pr?parate verloren dabei mehr
Wasser als bei gleicher Temperatur im Hochvakuum.
Die Ergebnisse und die Mechanismen der Ver?nderungen werden diskutiert.
Herrn Prof.U. Hofmann zum 60. Geburtstag gewidmet.
Herrn Prof. Dr.U. Hofmann sind wir für stete F?rderung und gro?zügige Unterstützung unserer Arbeiten zu gro?em Dank verpflichtet. Dem Fonds der Chemie und dem Landesgewerbeamt des Landes Baden-Württemberg danken wir für finanzielle Unterstützung. 相似文献
Summary The influence of various agents on the surface of Aerosil, a fine particle size silicia was studied. Originally, siloxane as well as silanol groups were present in the Aerosil surface. Partial hydrolysis of the siloxane bonds was achieved with cold water, ammoniacal pyrocatechol solution and after shorter contact with boiling water. The number of silanol groups per 100 ?2 never exceeded 3.3. On prolonged action of boiling water a significant decrease of the surface area and of the number of silanol groups was observed. Electron microphotographs show that the particles became coated by a layer of less dense porous silicia. As a result of the extremely narrow pores part of the surface and of the silanol groups escaped detection. Ammonia and, to a lesser extent, prolonged storing at atmospheric conditions had similar effects. At 200 °C the condensation of silanol groups to siloxane bonds was catalyzed by superheated steam as evidenced by a greater loss of silanol groups than in a high vacuum at the same temperature. The results and the mechanisms of the changes in the silica surface are discussed.
Herrn Prof.U. Hofmann zum 60. Geburtstag gewidmet.
Herrn Prof. Dr.U. Hofmann sind wir für stete F?rderung und gro?zügige Unterstützung unserer Arbeiten zu gro?em Dank verpflichtet. Dem Fonds der Chemie und dem Landesgewerbeamt des Landes Baden-Württemberg danken wir für finanzielle Unterstützung. 相似文献
15.
Hans‐Dietrich Stachel Barbara Zimmer Eduard Eckl Katharina Semmlinger Wolfgang Weigand Ralf Wünsch Peter Mayer 《Helvetica chimica acta》2005,88(6):1208-1220
The 1,2‐dithiolosultam derivative 14 was obtained from the (α‐bromoalkylidene)propenesultam derivative 9 (Scheme 1). Regioselective cleavage of the two ester groups (→ 1b or 2b ) allowed the preparation of derivatives with different substituents at C(3) in the dithiole ring (see 27 and 28 ) as well as at C(6) in the isothiazole ring (see 17 – 21 ; Scheme 2). Curtius rearrangement of the 6‐carbonyl azide 21 in Ac2O afforded the 6‐acetamide 22 , and saponification and decarboxylation of the latter yielded ‘sulfothiolutin’ ( 30 ). Hydride reductions of two of the bicyclic sultams resulted in ring opening of the sultam ring and loss of the sulfonyl group. Thus the reduction of the dithiolosultam derivative 14 yielded the alkylidenethiotetronic acid derivative 33 (tetronic acid=furan‐2,4(3H,4H)‐dione), and the lactam‐sultam derivative 10 gave the alkylidenetetramic acid derivative 35 (tetramic acid=1,5‐dihydro‐4‐hydroxy‐2H‐pyrrol‐2‐one) (Scheme 3). Some of the new compounds ( 14, 22, 26 , and 30 ) exhibited antimycobacterial activity. The oxidative addition of 1 equiv. of [Pt(η2‐C2H4)L2] ( 36a , L=PPh3; 36b , L=1/2 dppf; 36c , L=1/2 (R,R)‐diop) into the S? S bond of 14 led to the cis‐(dithiolato)platinum(II) complexes 37a – c . (dppf=1,1′‐bis(diphenylphosphino)ferrocene; (R,R)‐diop={[(4R,5R)‐2,2‐demithyl‐1,3‐dioxolane‐4,5‐diyl]bis(methylene)}bis[diphenylphosphine]). 相似文献
16.
17.
18.
John D. Mertens Katharina Kohse-Hinghaus Ronald K. Hanson Craig T. Bowman 《国际化学动力学杂志》1991,23(8):655-668
The reaction of atomic hydrogen with isocyanic acid (HNCO) to produce the amidogen radical (NH2) and carbon monoxide, has been studied in shock-heated mixtures of HNCO dilute in argon. Time-histories of the ground-state NH2 radical were measured behind reflected shock waves using cw, narrowlinewidth laser absorption at 597 nm, and HNCO time-histories were measured using infrared emission from the fundamental v2-band of HNCO near 5 μm. The second-order rate coefficient of reaction (2(a)) was determined to be: cm3 mol?1 s?1, where f and F define the lower and upper uncertainty limits, respectively. An upper limit on the rate coefficient of was determined to be: 相似文献
19.
20.
Novel l -tartaric acid based stereodynamic biphenylbisphosphinite ligands with anilino linkers were prepared as cyclic diamide compounds. The influence of the constitutional substitution pattern of the amino group at the aniline moiety on the diastereoselective formation of the ligand was investigated. While the meta-anilino bridged ligands showed a highly dynamic behavior and no discrimination between (Rax) and (Sax) configuration, l -tartaric acid substitution on ortho-anilino bridged ligands leads to diastereoselective self-alignment of the central biphenol axis, which controls the stereoselectivity of the ligand and catalyst. The experimental findings were corroborated by theoretical calculations. In the rhodium-catalyzed enantioselective hydrogenation of methyl 2-acetamidoacrylate (MAA), an enantiomeric ratio of 75 : 25 (R/S) was obtained for the ortho-substituted ligand. 相似文献