Theoretical study on reaction mechanism of the CF radical with nitrogen dioxide

Abstract

ABSTRACT:The singlet potential energy surface of the [CFNO 2 ] system is investigated at the B3LYP and CCSD(T) (single-point) levels to explore the possible reaction mechanism of CF radical with NO 2 . The top attack of C-atom of CF radical at the N-atom of NO 2 molecule first forms the adduct isomer FCNO 2 1 followed by oxygen-shift to give trans-OC(F)NO 2 and then to cis-OC(F)NO 3. Subsequently, the most favorable channel is a direct dissociation of 2 and 3 to product P 1 FCO + NO. The second and third less favorable channels are direct dissociation of 3 to product P 2 FNO + CO and isomerization of 3 to a complex NOF. . .CO 4, which can easily dissociate to product P 3 FON + CO, respectively. The large exothermicity released in these processes further drives most of the three products P 1 , P 2 , and P 3 to take secondary dissociation to the final product P 12 F + CO + NO. Another energetically allowed channel is formation of product P 4 1 NF + CO 2 , yet it is much less competitive than P 1 , P 2 , P 3 , and P 12 . The present calculations can well interpret one recent experimental fact that the title reaction is quite fast yet still much slower than the analogous reaction CH + NO 2 . Also, the results presented in this article may be useful for future product distribution analysis of the title reaction as well as for the analogous CCl and CBr reactions.

The Reaction of CO2 with a Borylnitrene: Formation of an 3‐Oxaziridinone

“…We here report for the first time the reaction of a borylnitrene with CO 2 and show that this results in an 1,2‐oxaziridin‐3‐one derivative [50] . These are the smallest possible cyclic carbamates, which were suggested as reactive intermediates [51–57] and have been studied computationally before, [58–61] but never could be isolated.…”

Theoretical study of 14N quadrupole coupling constants in some NO-containing complexes: N2O3 and FNO

“…The reason for these restrictions lies in the sizable dimension of the ASs which for the symmetry-and spin-adapted 1 A 0 state of N 2 O 3 leads to 1,074,585 and 2,864,950 configuration state functions, respectively. The respective ASs consist of 14 active orbitals with 16 active electrons, and of 15 active orbitals with 18 electrons, denoted in Tables 2 and 3 by short-hand notation as (16,14) and (18,15), respectively. Thus, in CASSCF calculations on N 2 O 3 no core correlation phenomena have been included, and from the use of core-valence basis sets no significant effects could be expected.…”

“…The first microwave spectroscopic studies of N 2 O 3 [4] and FNO [5], furnishing both structure parameters and nuclear quadrupole coupling constants (NQCCs), were reported almost forty years ago in the same issue of a journal. Since then a number of experimental and theoretical studies appeared on N 2 O 3 [6][7][8][9][10][11][12][13] and FNO [14][15][16][17][18][19] (and references therein) devoted to the interpretation and determination of structures, spectroscopic properties, dipole moments, heats of formation, etc., including those providing new 14 N QCCs on the basis of high-resolution measurements [1,20], and henceforth values of the electric field gradient (EFG) at nitrogen sites in N 2 O 3 . A theoretical investigation of the EFGs in N 2 O 3 is all the more desirable, because of the encountered problems with the analysis of the complex experimental hyperfine structure of rotational spectra arising from two non-equivalent nuclei [1,20] leading to the original misassignment of the two sets of 14 N coupling constants.…”

The Reaction of CO2 with a Borylnitrene: Formation of an 3‐Oxaziridinone

“…[35,42] A particular reactive derivative is super electrophilic difluorovinylidene that inserts into methane and dihydrogen at 20-40 K. [43][44][45][46][47][48][49] We here report for the first time the reaction of a borylnitrene with CO 2 and show that this results in an 1,2oxaziridin-3-one derivative. [50] These are the smallest possible cyclic carbamates, which were suggested as reactive intermediates [51][52][53][54][55][56][57] and have been studied computationally before, [58][59][60][61] but never could be isolated.…”

“…We here report for the first time the reaction of a borylnitrene with CO 2 and show that this results in an 1,2‐oxaziridin‐3‐one derivative. [50] These are the smallest possible cyclic carbamates, which were suggested as reactive intermediates[ 51 , 52 , 53 , 54 , 55 , 56 , 57 ] and have been studied computationally before,[ 58 , 59 , 60 , 61 ] but never could be isolated.…”