Gas-Phase Polymerization Reactions Induced by the C2H+m Ions (m=3-5) in Ethene.

Hiraoka, Kenzo; Kojima, Takanori; Sugiyama, Tomohisa; Katsuragawa, Jun

doi:10.5702/massspec.47.67

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“…Gas-phase ion−molecule reactions including saturated and unsaturated hydrocarbons have been the subject of many investigators. − In particular, the polymerization of C 2 H 4 induced by the primary C 2 H 4 + ion has been a topic of continuous and considerable interest for several decades. − ,, Kebarle and Haynes 2 showed that the reaction of C 2 H 4 + with C 2 H 4 molecules did not form cluster ions but rather formed covalently bonded molecular ions, C 2 H 4 + ·C 2 H 4 . The C 2 H 4 + ion readily underwent cationic polymerization of up to n = 4 monomers via sequential exothermic reactions.…”

Section: Introductionmentioning

confidence: 99%

“…Thus, the formation of the core pentamer cation with surrounding C 2 H 4 ligands, (C 2 H 4 ) 5 + ‚‚‚(C 2 H 4 ) n-5 was proposed. In our previous paper, 8 the reactions of C 2 H 3 + , C 2 H 4 + , and also C 2 H 5 + with C 2 H 4 as functions of the ion source temperature and the C 2 H 4 pressure were investigated. The larger polymerized ions were formed at lower temperature.…”

Section: Introductionmentioning

confidence: 99%

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Gas-Phase Ion−Molecule Reactions in C₃F₆

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6 ) n , respectively, become faster at lower temperature. This is due to the existence of an entropy barrier for the formation of cluster ions. The C 3 F 5 + ion was found to form cluster ions readily with C 3 F 6 solvent molecules. Thermochemical stabilities for C 3 F 5 + (C 3 F 6 ) n with n ) 1 and 2 could be determined. The proton affinity (PA) of C 3 F 6 was found to be smaller but close to that of C 2 H 4 (162.6 ( 1.5 kcal/mol). The G2MP2-calculated PA is 157.26 kcal/mol. Lone-pair orbitals of the CF 3 substituent are electronic-charge donor sites to C 2 F 4 + and C 3 F 5 + . The polymerization reactions of C 3 F 6 initiated by F -, C 3 F 5 -, and C 3 F 6were observed. Those reactions became faster with a decrease of temperature. The high reactivity of C 3 F 6 in the negative-mode ion/molecule reactions is ascribed to the perfluoro effect. The halide ions Cl -, Br -, and Iwere found to form cluster ions with C 3 F 6 . Thermochemical stabilities for X -(C 3 F 6 ) n (X -) Cl -, Br -, and I -) have been determined. A slight charge transfer in the complex Cl -fC 3 F 6 results in the fairly strong bond energy (12.6 kcal/mol) for the cluster.

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