FN+Cl Ions from Ionized F2NCl: a Computational Investigation on the Structure and Reactivity toward H2O
✍ Scribed by Stefano Borocci; Nicoletta Bronzolino; Felice Grandinetti
- Publisher
- John Wiley and Sons
- Year
- 2004
- Tongue
- German
- Weight
- 195 KB
- Volume
- 87
- Category
- Article
- ISSN
- 0018-019X
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✦ Synopsis
We have used various ab initio methods and basis sets to ascertain that the FN Cl cation has a singlet ground state, 1 A', which is more stable than the triplet state 3 A'' by ca. 30 kcal mol À1 . We have subsequently used the Gaussian-3 (G3) theory to explore the potential-energy profile for the reaction between singlet FN Cl and H 2 O. The process commences by the effortless formation of a FN Cl/H 2 O complex, which, in principle, can undergo several alternative processes, including isomerization to N-protonated FN(Cl)OH, 1,2-elimination of HX (X F or Cl), and 1,1-loss of H 2 . However, the energy barriers of all these processes are invariably larger than the energy ( 18.1 kcal mol À1 ) required for the formation of FN Cl/H 2 O from FN Cl and H 2 O, thus suggesting that, under gas-phase thermal conditions, FN Cl should be essentially unreactive toward H 2 O. Comparing these theoretical findings with those concerning the reaction between FN H, ClN H, F 2 N , and H 2 O, the reactivity order FN H > F 2 N > ClN H > FN Cl, was derived, which parallels the trend we recently found by G2MS calculations concerning the Lewis acidity of these ions. This suggests the conceivable occurrence of correlations between the reactivity and thermochemical properties of these simple halonitrenium ions.