Identification of Intermediates in the Photolysis of Mercaptans in Dilute Glass Matrices. II
| Autor: | Frank Cuthbert Adam, Allen John Elliot |
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| Rok vydání: | 1974 |
| Předmět: | |
| Zdroj: | Canadian Journal of Chemistry. 52:102-110 |
| ISSN: | 1480-3291 0008-4042 |
| DOI: | 10.1139/v74-015 |
| Popis: | Dilute solutions of aliphatic thiols have been prepared and photolyzed at 253.7 nm in 3-methylpentane glasses at 77°K. The major products formed initially are thiyl radicals RS• and hydrogen atoms. Both of these are hot and yield solvent radicals by abstraction reactions, and relatively small amounts of RS2•, RS•, and possibly R1R2C=S. Thermal annealing of the matrices is accompanied by loss of hydrocarbon radicals through cage reactions and concommitant increase in the RS• concentration. An intermediate radical of the type R1R2ĊSH may also be produced in the annealing process. The photometric and spin resonance characteristics of RS•, RS2•and R1ĊH—SH are discussed and related to other systems in which these intermediates are observed. RS• is characterized in the amorphous phase by an absorption at 405 nm and a broad asymmetrical e.p.r. resonance near [Formula: see text] RS2• has a non-axial g-tensor with principal values of about 2.06, 2.02, and 2.00 and has no detectable absorptions between 350 and 1200 nm.The photolytic behavior of these metastable radical species is also investigated. |
| Databáze: | OpenAIRE |
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