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Rates of Proton Abstraction from Conjugated Dienes in the Gas Phase
Author(s) -
Meyer Felix K.,
Pellerite Mark J.,
Brauman John I.
Publication year - 1981
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19810640411
Subject(s) - chemistry , cyclopentadiene , gas phase , proton , ion cyclotron resonance , reaction rate constant , resonance (particle physics) , molecule , acetone , computational chemistry , photochemistry , analytical chemistry (journal) , ion , atomic physics , organic chemistry , cyclotron , kinetics , nuclear physics , catalysis , physics , quantum mechanics
The rates of proton transfer from 2, 4‐hexadiene, 1, 3‐cycloheptadiene, cyclopentadiene and acetone to t ‐butoxide have been measured in the gas phase using pulsed‐ion‐cyclotron‐resonance spectroscopy. The rate constants are (units of 10 −10 cm 3 molecule −1 s −1 ): 2.7 ± 0.4, 3.8 ± 0.4, 6.1 ± 0.7 and 10.8 ± 1.5, respectively. These results are analyzed in terms of the properties of the encounter complex and reaction transition states. The reaction profile for t ‐butoxide + cyclopentadiene is modeled using RRKM theory and an estimate for the central barrier height is obtained.