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Antoniotti P, Benzi P, Borocci S, et al. Bimolecular Homolytic Substitutions at Nitrogen: An Experimental and Theoretical Study on the Gas-Phase Reactions of Alkyl Radicals with NF3. Chemistry. 2015;21(44):15826-34doi: 10.1002/chem.201501757.
Antoniotti, P., Benzi, P., Borocci, S., Demaria, C., Giordani, M., Grandinetti, F., Operti, L., & Rabezzana, R. (2015). Bimolecular Homolytic Substitutions at Nitrogen: An Experimental and Theoretical Study on the Gas-Phase Reactions of Alkyl Radicals with NF3. Chemistry (Weinheim an der Bergstrasse, Germany), 21(44), 15826-34. https://doi.org/10.1002/chem.201501757
Antoniotti, Paola, et al. "Bimolecular Homolytic Substitutions at Nitrogen: An Experimental and Theoretical Study on the Gas-Phase Reactions of Alkyl Radicals with NF3." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 21,44 (2015): 15826-34. doi: https://doi.org/10.1002/chem.201501757
Antoniotti P, Benzi P, Borocci S, Demaria C, Giordani M, Grandinetti F, Operti L, Rabezzana R. Bimolecular Homolytic Substitutions at Nitrogen: An Experimental and Theoretical Study on the Gas-Phase Reactions of Alkyl Radicals with NF3. Chemistry. 2015 Oct 26;21(44):15826-34. doi: 10.1002/chem.201501757. Epub 2015 Sep 08. PMID: 26345356.
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Chemistry. 2015 Oct 26;21(44):15826-34. doi: 10.1002/chem.201501757. Epub 2015 Sep 08.

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

Chemistry (Weinheim an der Bergstrasse, Germany)

Paola Antoniotti, Paola Benzi, Stefano Borocci, Chiara Demaria, Maria Giordani, Felice Grandinetti, Lorenza Operti, Roberto Rabezzana

Affiliations

  1. Dipartimento di Chimica, Università di Torino, Via P. Giuria 7, 10125 Torino (Italy). [email protected].
  2. Dipartimento di Chimica, Università di Torino, Via P. Giuria 7, 10125 Torino (Italy).
  3. Dipartimento per la Innovazione nei sistemi Biologici, Agroalimentari e Forestali (DIBAF), Università della Tuscia, L.go dell'Università, s.n.c. 01100 Viterbo (Italy).
  4. Istituto di Metodologie Chimiche, Area della Ricerca di Roma 1, Via Salaria Km 29?300, 00015 Monterotondo (Italy).

PMID: 26345356 DOI: 10.1002/chem.201501757

Abstract

The 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.

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: X-ray radiolysis; alkyl radicals; bimolecular reactions; density functional calculations; nitrogen trifluoride; substitution reactions

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