Relationships between DFT/RRKM branching ratios of the complementary fragment ions [C5H5O]+ and [M - C5H5O]+ and relative abundances in the EI mass spectrum of N-(2-furylmethyl)aniline.

The energy-dependent branching ratios of the complementary fragment ions [C(5)H(5)O](+) and [HC(6)H(4)NH](+) ([M - C(5)H(5)O](+)), originating from the N-(2-furylmethyl)aniline molecular ion, [HC(6)H(4)NH-C(5)H(5)O](+•), were obtained from Rice-Ramsperger-Kassel-Marcus (RRKM) rate calculations based on density functional theory (DFT) energy profiles. The UB3LYP/6-311G+(3df,2p)//UB3LYP/6-31G(d) level of theory was used to model the competitive reaction mechanisms by which the molecular ion can be fragmented. Initially, eight pairs of products were taken into account, corresponding to the combination of two isomeric structures for each fragment ion and the concomitant radicals, which can be formed by direct dissociations or through some isomerization-fragmentation pathways. A great deal of the obtained pathways was discarded by looking over the kinetic barrier heights and the individual RRKM rate coefficients calculated for all the steps. This way, the potential energy profiles were simplified to only three reaction channels, two pathways to [C(5)H(5)O](+) and one to [M - C(5)H(5)O](+). The pre-equilibrium and steady-state approximations were then applied to different regions of the remaining potential energy profiles, allowing the branching ratios of the complementary fragment ions to be easily calculated and discriminated among the three rival processes. According to these results, the major fragment ion in the ion source is [C(5)H(5)O](+), which is produced as a mixture of two structures, the furfuryl and pyrylium cations, one formed by a direct C-N bond cleavage and the other through an isomerization-fragmentation channel. In turn, the direct fragmentation is the only mechanism to produce [M - C(5)H(5)O](+). To confront these results with the available experimental information, the model was broadened out to the 4-substituted analogues [4-R-C(6)H(4)NH-C(5)H(5)O](+•) in which R = F, Br, Cl, CH(3), and OCH(3), finding excellent correlations of the calculated branching ratios and the relative abundances in the electron ionization mass spectra.

Linear free energy relationships in C-N bond dissociations in molecular ions of 4-substituted N-(2-furylmethyl)anilines in the gas phase.

The substituent effect on the reactivity of the C-N bond of molecular ions of 4-substituted N-(2-furylmethyl)anilines toward two dissociation pathways was studied. With this aim, six of these compounds were analyzed by mass spectrometry using electron ionization with energies between 7.8 and 69.9 eV. Also, the UB3LYP/6-31G (d,p) and UHF/6-31G (d, p) levels of theory were used to calculate the critical energies (reaction enthalpies at 0 K) of the processes that lead to the complementary ions [C(5)H(5)O](+) and [M - C(5)H(5)O](+), assuming structures that result from the heterolytic and homolytic C-N bond cleavages of the molecular ions, respectively. A kinetic approach proposed in the 1960s was applied to the mass spectral data to obtain the relative rate coefficients for both dissociation channels from ratios of the peak intensities of these ions. Linear relationships were obtained between the logarithms of the relative rate coefficients and the calculated critical energies and other thermochemical properties, whose slopes showed to be conditioned by the energy provided to the compounds within the ion source. Moreover, it was found that the dissociation that leads to [C(5)H(5)O](+) is a process strongly dependent upon the electron withdrawing or donating properties of the substituent, favored by those factors that destabilize the molecular ion. On the contrary, the dissociation that leads to [M - C(5)H(5)O](+) is indifferent to the polar electronic effects of the substituent. The abundance of both products was governed by the rule of Stevenson-Audier, according to which the major ion is the one of less negative electronic affinity.

Density functional theory and RRKM calculations of decompositions of the metastable E-2,4-pentadienal molecular ions.

The potential energy profiles for the fragmentations that lead to [C(5)H(5)O](+) and [C(4)H(6)](+*) ions from the molecular ions [C(5)H(6)O](+*) of E-2,4-pentadienal were obtained from calculations at the UB3LYP/6-311G + + (3df,3pd)//UB3LYP/6-31G(d,p) level of theory. Kinetic barriers and harmonic frequencies obtained by the density functional method were then employed in Rice-Ramsperger-Kassel-Marcus calculations of individual rate coefficients for a large number of reaction steps. The pre-equilibrium and rate-controlling step approximations were applied to different regions of the complex potential energy surface, allowing the overall rate of decomposition to be calculated and discriminated between three rival pathways: C-H bond cleavage, decarbonylation and cyclization. These processes should have to compete for an equilibrated mixture of four conformers of the E-2,4-pentadienal ions. The direct dissociation, however, can only become important in the high-energy regime. In contrast, loss of CO and cyclization are observable processes in the metastable kinetic window. The former involves a slow 1,2-hydrogen shift from the carbonyl group that is immediately followed by the formation of an ion-neutral complex which, in turn, decomposes rapidly to the s-trans-1,3-butadiene ion [C(4)H(6)](+*). The predominating metastable channel is the second one, that is, a multi-step ring closure which starts with a rate-limiting cis-trans isomerization. This process yields a mixture of interconverting pyran ions that dissociates to the pyrylium ions [C(5)H(5)O](+). These results can be used to rationalize the CID mass spectrum of E-2,4-pentadienal in a low-energy regime.

Density functional theory and RRKM calculations of the gas-phase unimolecular rearrangements of methylfuran and pyran ions before fragmentations.

The potential energy profiles for the mutual conversion of the isomeric molecular ions [C5H6O]+* of 2-methylfuran, 3-methylfuran and 4H-pyran and the fragmentations that lead to [C(5)H(5)O](+) ions were obtained from calculations at the B3LYP/6-311G++(3df,3pd)//B3LYP/6-31G(d,p) level of theory. The various competing unimolecular processes were characterized by their RRKM microcanonical rate coefficients, k(E), using the sets of reactant and transition state frequencies and the kinetic barriers obtained from the density functional method. In either a high- or a low-energy regime, the pyrylium ion [C5H5O]+ is generated directly from the 4H-pyran molecular ion by a simple cleavage. In contrast, in the metastable kinetic window, the molecular ions of methylfurans irreversibly isomerize to a mixture of interconverting structures before dissociation, which includes the 2H- and 3H-pyran ions. The hydrogen atoms attached to saturated carbons of the pyran rings are very stabilizing at the position 2, but they are very labile at position 3 and can be shifted to adjacent positions. Once 4H-pyran ion has been formed, the C-H bond cleavage begins before any hydrogen shift occurs. According to our calculation, there would not be complete H scrambling preceding the dissociation of the molecular ions [C5H6O]+*. On the other hand, as the internal energy of the 2-methylfuran molecular ion increases, H* loss can become more important. These results agree with the available experimental data.