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Single‐Electron Self‐Exchange between Cage Hydrocarbons and Their Radical Cations in the Gas Phase
Author(s) -
Guerrero Andrés,
Herrero Rebeca,
Quintanilla Esther,
Dávalos Juan Z.,
Abboud JoséLuis M.,
Coto Pedro B.,
Lenoir Dieter
Publication year - 2010
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200900824
Subject(s) - chemistry , reaction rate constant , electron transfer , ab initio quantum chemistry methods , radical ion , gas phase , ab initio , computational chemistry , ion , reaction mechanism , adamantane , molecule , kinetics , organic chemistry , physics , quantum mechanics , catalysis
We show that the radical cations of adamantane (C 10 H 16 .+ , 1 H .+ ) and perdeuteroadamantane (C 10 D 16 .+ , 1 D .+ ) are stable species in the gas phase. The radical cation of adamantylideneadamantane (C 20 H 28 .+ , 2 H .+ ) is also stable (as in solution). By using the natural 13 C abundances of the ions, we determine the rate constants for the reversible isergonic single‐electron transfer (SET) processes involving the dyads 1 H .+ / 1 H, 1 D .+ / 1 D and 2 H .+ / 2 H. Rate constants for the reaction 1 H .+ + 1 D⇄ 1 H+ 1 D .+ are also determined and Marcus’ cross‐term equation is shown to hold in this case. The rate constants for the isergonic processes are extremely high, practically collision‐controlled. Ab initio computations of the electronic coupling ( H DA ) and the reorganization energy ( λ ) allow rationalization of the mechanism of the process and give insights into the possible role of intermediate complexes in the reaction mechanism.