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• 187737-37-7 propene 
• 108-88-3 toluene radical cation 
• 71-43-2 benzene radical cation 
• 111-65-9 octane radical cation 

Relevant academic research and scientific papers

Coupled reactions of condensation and charge transfer. 1. Formation of olefin dimer ions in reactions with ionized aromatics. Gas-phase studies

The toluene radical ion C6H5CH3(·)+, generated by resonance two-photon ionization, does not react with a single isobutene molecule (i-C4H8) which has a significantly higher ionization potential (ΔIP = 0.42 eV). However, a reaction is observed involving two i-C4H8 molecules, to form the dimer ion C8H16(·)+. A coupled reaction of dimer formation and charge transfer to the dimer is exothermic if the product is an ionized hexene with a low IF. Correspondingly, the observed nominal second-order rate coefficients, (5-25) x 10-12 cm3 s-1, are enhanced by a factor of > 105 over the expected value for direct endothermic charge transfer. Pressure and concentration effects suggest a sequential mechanism that proceeds through a C6H5CH3·+(i-C4H8) reactive π complex. The complex can isomerize to a nonreactive CH3C6H4-t-C4H9(·)+ adduct,or react with a second i-C4H8 molecule to form a C6H5CH3·+-(i-C4H8)2 complex, in which the olefin molecules are activated by the aromatic ion. Similar reactions are observed in the benzene/propene system with a somewhat larger ΔIP of 0.48 eV, suggesting that the charge density on the olefin in the complex is still sufficient to activate it for nucleophilic attack. However, aromatic/olefin systems with ΔIP > 0.87 eV show no olefin dimer formation. At low [i-C4H8] and [Ar] number densities, the rate of formation of C8H16(·)+ is proportional to [i-C4H8]2[Ar]. The corresponding fourth-order rate coefficient shows a strong negative temperature coefficient with k = 11 x 10-42 cm9 s-1 at 300 K and 2 x 10-42 cm9 s-1 at 346 K, suggesting that the mechanism can be efficient in low-temperature industrial and interstellar environments. The direct formation of the dimer bypasses the monomer olefin cation and its consequent side-reactions, and directs the products selectively into radical ion polymerization. The products and energy relationships that apply in the gas phase are observed also in clusters.

Ion-Molecule Reactions and Thermal Decomposition of Ions in N2-O2-Alkane (C2-C8) Mixtures Studied by Time-Resolved Atmospheric Pressure Ionization Mass

The experiments were carried out at temperatures ranging from 236 to 569 K.The O2+ ion reacted with n-alkanes (CnH2n+2) via fast nondissociative and dissociative charge-transfer channels, its proportion depending on temperature.The nondissociative product CnH(2n+2)+ subsequently reacted with O2 via a slow H atom transfer path, producing alkyl ions.With increasing temperature the alkane ions CnH(2n+2)+ (n >/= 4) began to decompose thermally, producing olefinic ions and alkanes.The product olefinic ions CmH2m+ (m=4,5,6) reacted with O2 via a slow H atom transfer path, producing alkenyl ions CmH(2m-1)+.The C8H17+ decomposed thermally forming fragment alkyl ions and olefins.The fragment alkyl ions reacted with n-C8H18 reproducing C8H17+, thus leading to a chain mechanism in n-C8H18 decomposition.The equilibrium reaction, C2H5+ + C2H6 ->/+, and the subsequent dissociative rearrangement reaction, C4H11+ -> C4H9+ + H2, were studied.The reactions of NO+ and NOO+, both minor products of the irradiation of N2-O2 mixtures, with alkanes were also studied.The rate constants of the ion-molecule reactions and the unimolecular thermal decomposition reactions and the equilibrium constant were measured.