Carbon-13 Kinetic Isotope Effects in the Catalytic Oxidation of Carbon Monoxide Over Pd/Al2O3

1997 ◽  
Vol 101 (39) ◽  
pp. 7236-7242 ◽  
Author(s):  
Nives Ogrinc ◽  
Ivan Kobal ◽  
Marjan Senegačnik
Keyword(s):  
Carbon Monoxide ◽  
Catalytic Oxidation ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Oxidation Of Carbon Monoxide

The thermally induced rearrangements of 2-vinyloxirane

1976 ◽  
Vol 54 (21) ◽  
pp. 3364-3376 ◽  
Author(s):  
Robert J. Crawford ◽  
Stuart B. Lutener ◽  
Robert D. Cockcroft
Keyword(s):  
Carbon Monoxide ◽  
Gas Phase ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Thermally Induced ◽  
Rate Determining Step ◽  
Kinetic Isotope ◽  
Carbonyl Ylide ◽  
Structural Isomerization ◽  
Kinetics Of

The kinetics of the gas phase thermolysis of 2-vinyloxirane (4) have been studied over the temperature range 270–310 °C. The racemization of chiral 4 occurs six times faster than the structural isomerization to 2,3-dihydrofuran, (E)- and (Z)-2-butenal, and 3-butenal. The butenals undergo a slow thermolysis to propene and carbon monoxide. cis-Deuterio- and trans-3-deuterio-vinyloxirane have been synthesized and their interconversion is slow. Deuterium kinetic isotope effects on mono- and dideuterio-4 suggest that for the formation of the butenals the rate determining step involves rupture of the oxirane C—O bond. The dihydrofuran is produced by thermolysis of the oxirane C—C bond. The preferred mechanistic interpretation is that a carbon–oxygen diradical serves as an intermediate for butenal formation, and that a carbonyl-ylide is involved in the formation of the dihydrofuran.The relative rates, at 307.4 °C, of cis–trans-5-isomerization:dihydrofuran formation:racemization: butenal formation for 3-deuterio-2-vinyloxirane are 1.0:0.88:40.2:5.94, respectively.

Carbon-13 Kinetic Isotope Effects in the Catalytic Oxidation of CO over Ag

1998 ◽  
Vol 102 (35) ◽  
pp. 6787-6791 ◽  
Author(s):  
Ivan Kobal ◽  
Uwe Burghaus ◽  
Marjan Senegačnik ◽  
Nives Ogrinc
Keyword(s):  
Catalytic Oxidation ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Oxidation Of Co ◽  
Kinetic Isotope ◽  
Catalytic Oxidation Of Co

Theoretical Simulations of Heavy-Atom Kinetic Isotope Effects in Aliphatic Claisen Rearrangement

2020 ◽  
Vol 124 (51) ◽  
pp. 10678-10686
Author(s):  
Yuqing Xu ◽  
Kin-Yiu Wong ◽  
Meishan Wang ◽  
Desheng Liu ◽  
Wenkai Zhao ◽  
...  
Keyword(s):  
Claisen Rearrangement ◽  
Isotope Effects ◽  
Heavy Atom ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Theoretical Simulations
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