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Unsaturated Vinyl-Type Carbocation [(CH₃)₂C=CH]⁺ in Its Carborane Salts.

ABSTRACT: The isobutylene carbocation (CH₃)₂C=CH⁺ was obtained in amorphous and crystalline salts with the carborane anion CHB₁₁Cl₁₁ ^-. The cation was characterized by X-ray crystallography and IR spectroscopy. Its crystal structure shows a relatively uniform ionic interaction of the cation with the surrounding anions, with a slightly shortened distance between the C atom of the =CH group and the Cl atom of the anion, pointing to a higher positive charge on this group. In the amorphous phase, the asymmetric interaction of the cation with the anion increases, approaching ion pairing. This gives rise to a strong hyperconjugation between the two CH₃ groups and the 2p_z orbital of the central carbon sp² atom (the red shift of the CH stretch is 150 cm^-1); this effect stabilizes the cation. Over time, as the structure of the amorphous phase becomes more ordered, the hyperconjugation weakens and disappears in the crystalline phase with the disappearance of ion pairing. The carbocation stabilization in the crystalline phase is achieved due to the transfer of a portion of the charge to the neighboring anions, whereas the charge on the C=C bond becomes the strongest: the C=C stretch frequency drops to ∼160 cm^-1 relative to neutral isobutylene. The collected IR spectra for the optimized cation under vacuum (in the 6-311G ++ (d, p) basis for all HF, MP2, and DFT calculations) predict that a positive charge on the C=C bond increases its stretching frequency; this computational result contradicts the experimental data, perhaps because it does not take into account the significant impact of the environment.

SUBMITTER: Stoyanov ES

PROVIDER: S-EPMC8223440 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The reaction of electronically excited nitrogen atoms, N(2D), with vinyl cyanide, CH2CHCN, has been investigated under single-collision conditions by the crossed molecular beam (CMB) scattering method with mass spectrometric detection and time-of-flight (TOF) analysis at the collision energy, Ec, of 31.4 kJ/mol. Synergistic electronic structure calculations of the doublet potential energy surface (PES) have been performed to assist in the interpretation of the experimental results and characterize the overall reaction micromechanism. Statistical (Rice-Ramsperger-Kassel-Marcus, RRKM) calculations of product branching fractions (BFs) on the theoretical PES have been carried out at different values of temperature, including the one corresponding to the temperature (175 K) of Titan's stratosphere and at a total energy corresponding to the Ec of the CMB experiment. According to our theoretical calculations, the reaction is found to proceed via barrierless addition of N(2D) to the carbon-carbon double bond of CH2═CH-CN, followed by the formation of cyclic and linear intermediates that can undergo H, CN, and HCN elimination. In competition, the N(2D) addition to the CN group is also possible via a submerged barrier, leading ultimately to N2 + C3H3 formation, the most exothermic of all possible channels. Product angular and TOF distributions have been recorded for the H-displacement channels leading to the formation of a variety of possible C3H2N2 isomeric products. Experimentally, no evidence of CN, HCN, and N2 forming channels was observed. These findings were corroborated by the theory, which predicts a variety of competing product channels, following N(2D) addition to the double bond, with the main ones, at Ec = 31.4 kJ/mol, being six isomeric H forming channels: c-CH(N)CHCN + H (BF = 35.0%), c-CHNCHCN + H (BF = 28.1%), CH2NCCN + H (BF = 26.3%), c-CH2(N)CCN(cyano-azirine) + H (BF = 7.4%), trans-HNCCHCN + H (BF = 1.6%), and cis-HNCCHCN + H (BF = 1.3%), while C-C bond breaking channels leading to c-CH2(N)CH(2H-azirine) + CN and c-CH2(N)C + HCN are predicted to be negligible (0.02% and 0.2%, respectively). The highly exothermic N2 + CH2CCH (propargyl) channel is also predicted to be negligible because of the very high isomerization barrier from the initial addition intermediate to the precursor intermediate able to lead to products. The predicted product BFs are found to have, in general, a very weak energy dependence. The above cyclic and linear products containing an additional C-N bond could be potential precursors of more complex, N-rich organic molecules that contribute to the formation of the aerosols on Titan's upper atmosphere. Overall, the results are expected to have a significant impact on the gas-phase chemistry of Titan's atmosphere and should be properly included in the photochemical models.

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Unsaturated Vinyl-Type Carbocation [(CH₃)₂C=CH]⁺ in Its Carborane Salts.

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Unsaturated Vinyl-Type Carbocation [(CH3)2C=CH]+ in Its Carborane Salts.

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Unsaturated Vinyl-Type Carbocation [(CH₃)₂C=CH]⁺ in Its Carborane Salts.