he X-ray irradiation of binary mixtures of alkyl iodides R-I (R=CH3 , C2 H5 , or i-C3 H7 radicals) and NF3 produces R-NF2 and R-F. Based on calculations performed at the CCSD(T), MRCI(SD+Q), G3B3, and G3 levels of theory, the former product arises from a bimolecular homolytic substitution reaction (SH 2) by the alkyl radicals R, which attack the N atom of NF3 . This mechanism is consistent with the suppression of R-NF2 by addition of O2 (an efficient alkyl radical scavenger) to the reaction mixture. The R-F product arises from the attack of R to the F atom of NF3 , but additional contributing channels are conceivably involved. The F-atom abstraction is, indeed, considerably more exothermic than the SH 2 reaction, but the involved energy barriers are comparable, and the two processes are comparably fast.

Bimolecular Homolytic Substitutions at Nitrogen: An Experimental and Theoretical Study on the Gas-Phase Reactions of Alkyl Radicals with NF3

ANTONIOTTI, Paola;BENZI, Paola;DEMARIA, Chiara;OPERTI, Lorenza;RABEZZANA, Roberto
2015

Abstract

he X-ray irradiation of binary mixtures of alkyl iodides R-I (R=CH3 , C2 H5 , or i-C3 H7 radicals) and NF3 produces R-NF2 and R-F. Based on calculations performed at the CCSD(T), MRCI(SD+Q), G3B3, and G3 levels of theory, the former product arises from a bimolecular homolytic substitution reaction (SH 2) by the alkyl radicals R, which attack the N atom of NF3 . This mechanism is consistent with the suppression of R-NF2 by addition of O2 (an efficient alkyl radical scavenger) to the reaction mixture. The R-F product arises from the attack of R to the F atom of NF3 , but additional contributing channels are conceivably involved. The F-atom abstraction is, indeed, considerably more exothermic than the SH 2 reaction, but the involved energy barriers are comparable, and the two processes are comparably fast.
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http://onlinelibrary.wiley.com/doi/10.1002/chem.201501757/full
X-ray radiolysis; alkyl radicals; bimolecular reactions; density functional calculations; nitrogen trifluoride; substitution reactions
Antoniotti, Paola; Benzi, Paola; Borocci, Stefano; Demaria, Chiara; Giordani, Maria; Grandinetti, Felice; Operti, Lorenza; Rabezzana, Roberto
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/1524250
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