Dataset Information

Protonation of Borylated Carboxonium Derivative [2,6-B₁₀H₈O₂CCH₃]^-: Theoretical and Experimental Investigation.

ABSTRACT: The process of protonation of [2,6-B₁₀H₈O₂CCH₃]^- was investigated both theoretically and experimentally. The most suitable conditions for protonation of the derivative [2,6-B₁₀H₈O₂CCH₃]^- were found. The process of protonation was carried out in the presence of an excess of trifluoromethanesulfonic acid CF₃SO₃H at room temperature in dichloromethane solution. The structure of the resulting complex [2,6-B₁₀H₈O₂CCH₃*H^fac]⁰ was established using NMR data and the results of DFT calculations. An additional proton atom H^fac was found to be localized on one of the facets that was opposite the boron atom in a substituted position, and which bonded mainly with one apical boron atom. The main descriptors of the B-H^fac bond were established theoretically using QTAIM and NBO approaches. In addition, the mechanism of [2,6-B₁₀H₈O₂CCH₃]^- protonation was investigated.

SUBMITTER: Klyukin IN

PROVIDER: S-EPMC9025682 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature

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Publications

Protonation of Borylated Carboxonium Derivative [2,6-B10H8O2CCH3]-: Theoretical and Experimental Investigation.

Klyukin Ilya N IN Kolbunova Anastasia V AV Novikov Alexander S AS Nelyubin Aleksey V AV Selivanov Nikita A NA Bykov Alexander Yu AY Klyukina Alexandra A AA Zhdanov Andrey P AP Zhizhin Konstantin Yu KY Kuznetsov Nikolay T NT

International journal of molecular sciences 20220410 8

The process of protonation of [2,6-B10H8O2CCH3]- was investigated both theoretically and experimentally. The most suitable conditions for protonation of the derivative [2,6-B10H8O2CCH3]- were found. The process of protonation was carried out in the presence of an excess of trifluoromethanesulfonic acid CF3SO3H at room temperature in dichloromethane solution. The str ...[more]

PMID: 35457007

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Project description:The reaction of excited nitrogen atoms N(2D) with CH3CCH (methylacetylene) was investigated under single-collision conditions by the crossed molecular beams (CMB) scattering method with mass spectrometric detection and time-of-flight analysis at the collision energy (Ec) of 31.0 kJ/mol. Synergistic electronic structure calculations of the doublet potential energy surface (PES) were performed to assist the interpretation of the experimental results and characterize the overall reaction micromechanism. Theoretically, the reaction is found to proceed via a barrierless addition of N(2D) to the carbon-carbon triple bond of CH3CCH and an insertion of N(2D) into the CH bond of the methyl group, followed by the formation of cyclic and linear intermediates that can undergo H, CH3, and C2H elimination or isomerize to other intermediates before unimolecularly decaying to a variety of products. Kinetic calculations for addition and insertion mechanisms and statistical (Rice-Ramsperger-Kassel-Marcus) computations of product branching fractions (BFs) on the theoretical PES were performed at different values of total energy, including the one corresponding to the temperature (175 K) of Titan's stratosphere and that of the CMB experiment. Up to 14 competing product channels were statistically predicted, with the main ones, at Ec = 31.0 kJ/mol, being the formation of CH2NH (methanimine) + C2H (ethylidyne) (BF = 0.41), c-C(N)CH + CH3 (BF = 0.32), CH2CHCN (acrylonitrile) + H (BF = 0.12), and c-CH2C(N)CH + H (BF = 0.04). Of the 14 possible channels, seven correspond to H displacement channels of different exothermicity, for a total H channel BF of ∼0.25 at Ec = 31.0 kJ/mol. Experimentally, dynamical information could only be obtained about the overall H channels. In particular, the experiment corroborates the formation of acrylonitrile + H, which is the most exothermic of all 14 reaction channels and is theoretically calculated to be the dominant H-forming channel (BF = 0.12). The products containing a novel C-N bond could be potential precursors to form other nitriles (C2N2, C3N) or more complex organic species containing N atoms in planetary atmospheres, such as those of Titan and Pluto. Overall, the results are expected to have a potentially significant impact on the understanding of the gas-phase chemistry of Titan's atmosphere and the modeling of that atmosphere.

Dataset Information

Protonation of Borylated Carboxonium Derivative [2,6-B₁₀H₈O₂CCH₃]^-: Theoretical and Experimental Investigation.

Publications

Protonation of Borylated Carboxonium Derivative [2,6-B<sub>10</sub>H<sub>8</sub>O<sub>2</sub>CCH<sub>3</sub>]<sup>-</sup>: Theoretical and Experimental Investigation.

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