Matrix-isolated trifluoromethylthiyl radical: sulfur atom transfer, isomerization and oxidation reactions

2021 ◽  
Author(s):  
Bifeng Zhu ◽  
Zhuang Wu ◽  
Lina Wang ◽  
Tarek Trabelsi ◽  
Joseph S. Francisco ◽  
...  
Keyword(s):  
Gas Phase ◽  
Sulfur Atom ◽  
High Vacuum ◽  
Atom Transfer ◽  
Oxidation Reactions ◽  
Flash Pyrolysis

By high-vacuum flash pyrolysis of bis(trifluoromethyl)disulfane oxide (CF3S(O)SCF3) at 400 °C, the elusive trifluoromethylthiyl radical (CF3S•) has been efficiently generated in the gas phase. Subsequent isolation of CF3S• in cryogenic...

Spectroscopic Characterization and Photochemistry of the Vinylsulfinyl Radical

2021 ◽  
Author(s):  
Zhuang Wu ◽  
Lina Wang ◽  
Bo Lu ◽  
André K. Eckhardt ◽  
Peter Richard Schreiner ◽  
...  
Keyword(s):  
Gas Phase ◽  
High Vacuum ◽  
Spectroscopic Characterization ◽  
Flash Pyrolysis ◽  
Sulfinyl Radical ◽  
Cis And Trans

The simplest α,β-unsaturated sulfinyl radical CH2=C(H)SO• has been generated in the gas phase by high-vacuum flash pyrolysis (HVFP) of sulfoxide CH2=C(H)S(O)CF3 at ca. 800 °C. Two planar cis and trans...

Chemisorption of ethylene on nickel surfaces with preadsorbed oxygen

1981 ◽  
Vol 46 (2) ◽  
pp. 340-353
Author(s):  
Pavel Zachař ◽  
Zdeněk Bastl ◽  
Jakub Adámek
Keyword(s):  
Gas Phase ◽  
Phase Analysis ◽  
Oxygen Concentration ◽  
Electrical Resistance ◽  
High Vacuum ◽  
Volumetric Method ◽  
Surface Oxygen ◽  
Oxygen Chemisorption ◽  
Thin Polycrystalline ◽  
Total Adsorption

Chemisorption of ethylene was studied on thin polycrystalline layers of nickel prepared by metal deposition in high vacuum and modified by preadsorbed oxygen. The volumetric method combined with the gas-phase analysis and the measurement of the electrical resistance changes of these layers were used. Already small amounts of preadsorbed oxygen of the order of 10-2 of the monolayer affect rather substantially the extent of ethylene chemisorption. The extent of the initial irreversible chemisorption and also the total adsorption of ethylene as a function of the amount of preadsorbed oxygen have a maximum at the surface oxygen concentration of 3 . 1013 molecule cm-2. The adsorption accompanied by the extensive dissociation of ethylene C-H bonds proceeds predominantly on nickel atoms with lower coordination (atoms on the microcrystal edges, corner atoms, etc.), where also oxygen chemisorption proceeds preferentially.

Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation

2021 ◽  
Vol 23 (11) ◽  
pp. 6462-6471
Author(s):  
Piyush Mishra ◽  
Sean M. Fritz ◽  
Sven Herbers ◽  
Alexander M. Mebel ◽  
Timothy S. Zwier
Keyword(s):  
Gas Phase ◽  
Molecular Beam ◽  
Microwave Spectroscopy ◽  
Radical Species ◽  
Flash Pyrolysis

The flash pyrolysis of trans 3-pentenenitrile was studied by mass-correlated broadband microwave spectroscopy, where both molecular and radical species were observed within our jet-cooled molecular beam, including 2,4-pentadienenitrile.

Gas phase interaction with catalytic oxidation reactions

1972 ◽  
Vol 326 (1565) ◽  
pp. 215-227 ◽  
Keyword(s):  
Carbon Dioxide ◽  
Maleic Anhydride ◽  
Catalytic Oxidation ◽  
Gas Phase ◽  
Major Part ◽  
Oxidation Reactions ◽  
Mixed Gas ◽  
Kinetics Of ◽  
Oxidation Of Benzene ◽  
Homogeneous Decomposition

Studies of the catalytic oxidation of benzene to maleic anhydride and carbon dioxide over vanadia/molybdena catalysts show that the major part of the reaction involves interacting gas and gas-solid processes. The results are consistent with a mechanism in which a benzeneoxygen adduct is formed catalytically, desorbs and then reacts to give maleic anhydride entirely in the gas phase. On the basis of this proposed mechanism, the kinetics of individual reactions have been investigated in some depth. The over-oxidation of maleic anhydride has been found to be not significant under the conditions of reaction. The kinetic relationships governing the homogeneous decomposition of the adduct and the oxidation of the adduct to maleic anhydride and to carbon dioxide have been established. The results show that essentially all of the anhydride originates from mixed gas-solid/gas reaction while substantial amounts of carbon dioxide are produced entirely catalytically.

Metal–Ligand Cooperativity Promoting Sulfur Atom Transfer in Ferrous Complexes and Isolation of a Sulfurmethylenephosphorane Adduct

2018 ◽  
Vol 57 (18) ◽  
pp. 11552-11559 ◽  
Author(s):  
Dieter Sorsche ◽  
Matthias E. Miehlich ◽  
Eva M. Zolnhofer ◽  
Patrick J. Carroll ◽  
Karsten Meyer ◽  
...  
Keyword(s):  
Sulfur Atom ◽  
Atom Transfer ◽  
Metal Ligand

scholarly journals Probing ‘Spin-Forbidden’ Oxygen-Atom Transfer: Gas-Phase Reactions of Chromium−Porphyrin Complexes

2010 ◽  
Vol 132 (12) ◽  
pp. 4336-4343 ◽  
Author(s):  
Maria Elisa Crestoni ◽  
Simonetta Fornarini ◽  
Francesco Lanucara ◽  
Jeffrey J. Warren ◽  
James M. Mayer
Keyword(s):  
Oxygen Atom ◽  
Gas Phase ◽  
Atom Transfer ◽  
Oxygen Atom Transfer ◽  
Gas Phase Reactions

scholarly journals Dioxygen dissociation over man-made system at room temperature to form the active α-oxygen for methane oxidation

2020 ◽  
Vol 6 (20) ◽  
pp. eaaz9776 ◽  
Author(s):  
Edyta Tabor ◽  
Jiri Dedecek ◽  
Kinga Mlekodaj ◽  
Zdenek Sobalik ◽  
Prokopis C. Andrikopoulos ◽  
...  
Keyword(s):  
Gas Phase ◽  
Room Temperature ◽  
Practical Importance ◽  
Oxidation Reactions ◽  
Reaction Conditions ◽  
Oxidation Of Methane ◽  
Oxidation Properties ◽  
Enzyme Functionality ◽  
Methane Utilization ◽  
Selective Oxidation Reactions

Activation of dioxygen attracts enormous attention due to its potential for utilization of methane and applications in other selective oxidation reactions. We report a cleavage of dioxygen at room temperature over distant binuclear Fe(II) species stabilized in an aluminosilicate matrix. A pair of formed distant α-oxygen species [i.e., (Fe(IV)═O)2+] exhibits unique oxidation properties reflected in an outstanding activity in the oxidation of methane to methanol at room temperature. Designing a man-made system that mimicks the enzyme functionality in the dioxygen activation using both a different mechanism and structure of the active site represents a breakthrough in catalysis. Our system has an enormous practical importance as a potential industrial catalyst for methane utilization because (i) the Fe(II)/Fe(IV) cycle is reversible, (ii) the active Fe centers are stable under the reaction conditions, and (iii) methanol can be released to gas phase without the necessity of water or water-organic medium extraction.

Mechanistic Aspects of Gas-Phase Hydrogen-Atom Transfer from Methane to [CO].+and [SiO].+: Why Do They Differ?

2013 ◽  
Vol 19 (21) ◽  
pp. 6662-6669 ◽  
Author(s):  
Nicolas Dietl ◽  
Anna Troiani ◽  
Maria Schlangen ◽  
Ornella Ursini ◽  
Giancarlo Angelini ◽  
...  
Keyword(s):  
Hydrogen Atom ◽  
Gas Phase ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer
Sign in / Sign up

Export Citation Format

Share Document