Radical reactions in a single crystal of phosphaalkene: EPR and ab initio calculations of phosphoniumyl radical cations

1995 ◽  
Vol 99 (43) ◽  
pp. 15864-15869 ◽  
Author(s):  
Shrinivasa N. Bhat ◽  
Theo Berclaz ◽  
Michel Geoffroy ◽  
Abdelaziz Jouaiti
Keyword(s):  
Ab Initio Calculations ◽  
Single Crystal ◽  
Ab Initio ◽  
Radical Cations ◽  
Radical Reactions

Cleavage of the radical cations of alkenes; 1-butene and 4,4-dimethyl-1-pentene. Ab initio calculations on the interaction between the allyl and alkyl radical and carbocation moieties

1991 ◽  
Vol 69 (9) ◽  
pp. 1365-1375 ◽  
Author(s):  
Xinyao Du ◽  
Donald R. Arnold ◽  
Russell J. Boyd ◽  
Zheng Shi
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Radical Cation ◽  
Alkyl Radical ◽  
Radical Cations ◽  
Molecular Orbital Calculations ◽  
Allyl Radical ◽  
Allyl Cation ◽  
Tert Butyl ◽  
Carbon Carbon Bond

Carbon–carbon bond cleavage of the radical cations of 1-butene [Formula: see text] and 4,4-dimethyl-1-pentene [Formula: see text] will generate the allyl and alkyl radical and carbocation fragments. Alternative bonding arrangements between the allyl and methyl moieties in [Formula: see text] and between the allyl and tert-butyl moieties in [Formula: see text] possible metastable intermediates or transition states preceding complete separation of the fragments, have been investigated by ab initio molecular orbital calculations. Structures were fully optimized at the UHF/6-31G* or UHF/STO-3G levels, and some of the calculations on [Formula: see text] were expanded with single point MP2/6-31G*//UHF/6-31G* computations. The C4H8+ radical cation, having a structure similar to that of 1-butene, is more stable than the separated fragments: 183 kj mol−1 lower in energy than the sum of the energies of the allyl cation and the methyl radical, and 385 kJ mol−1 lower than the sum of the energies of an allyl radical and a methyl cation, at the MP2/6-31G* level. The corresponding values at the UHF/STO-3G level are 276 and 415 kj mol−1, respectively. There is less bonding interaction between the allyl and tert-butyl moieties in [Formula: see text] The summation of the energies of the allyl radical and tert-butyl cation is 123 kj mol−1 lower than the summation of the energies of the allyl cation and tert-butyl radical, and 115 kJ mol−1 higher in energy than the bonded radical cation [Formula: see text] at the UHF/STO-3G level. These calculated values are compared with thermochemical data and with experimental results on the cleavage of these, and related, radical cations. Key words: radical cation, cleavage, ab initio calculations, electron transfer, photochemistry.

The structure of diphosphaallenic radical cations as evidenced by EPR experiments and ab initio calculations

1997 ◽  
pp. 921-926 ◽  
Author(s):  
Mostafa Chentit ◽  
Helena Sidorenkova ◽  
Abdelaziz Jouaiti ◽  
Gustavo Terron ◽  
Michel Geoffroy ◽  
...  
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Radical Cations ◽  
Epr Experiments
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