Product-resolved photodissociations of iodotoluene radical cations
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- Title
- Product-resolved photodissociations of iodotoluene radical cations
- Authors
- Shin, SK; Kim, B; Jarek, RL; Han, SJ
- Date Issued
- 2002-02-20
- Publisher
- KOREAN CHEMICAL SOC
- Abstract
- Photodissociations of o-, m-, and p-iodotoluene radical cations were investigated by using Fourier-transform ion cyclotron resonance (FT-ICR) spectrometry. Iodotoluene radical cations were prepared in an ICR cell by a photoionization charge-transfer method. The time-resolved one-photon dissociation spectra were obtained at 532 nm and the identities of C7H7+ products were determined by examining their bimolecular reactivities toward toluene-d(8). The two-photon dissociation spectra were also recorded in the wavelength range 615-670 nm. The laser power dependence, the temporal variation, and the identities of C7H7+ were examined at 640 nm. The mechanism of unimolecular dissociation of iodotoluene radical cations is elucidated: the lowest barrier rearrangement channel leads exclusively to the formation of the benzylcation, whereas the direct C-I cleavage channel yields the tolyl cations that rearrange to both benzyl and tropylium cations with dissimilar branching ratios among o-, m-, and p-isomers. With a two-photon energy of 3.87 eV at 640 nm, the direct C-I cleavage channel results in the product branching ratio, [tropylium cation]/[benzyl cation], in descending order, 0.16 for meta > 0.09 for ortho > 0.05 for para.
- Keywords
- FT-ICR; time-resolved photodissociation; iodotoluene; tolyl cation; product-resolved photodissociation; COLLISIONAL ACTIVATION; MASS-SPECTRA; ION; TOLUENE; BENZYL; TOLYL; PROBE
- URI
- https://oasis.postech.ac.kr/handle/2014.oak/19185
- DOI
- 10.5012/bkcs.2002.23.2.267
- ISSN
- 0253-2964
- Article Type
- Article
- Citation
- BULLETIN OF THE KOREAN CHEMICAL SOCIETY, vol. 23, no. 2, page. 267 - 270, 2002-02-20
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