Photochemistry of trimethylene oxide and trimethylene sulfide radical cations in freonic matrices at 77 K

被引：4

作者：

Mel'nikov, M. Ya. ^{[1
]}

Kalugina, A. D. ^{[1
]}

Mel'nikova, O. L. ^{[1
]}

Pergushov, V. I. ^{[1
]}

Tyurin, D. A. ^{[1
]}

机构：

[1] Moscow MV Lomonosov State Univ, Moscow 119991, Russia

来源：

HIGH ENERGY CHEMISTRY | 2009年 / 43卷 / 04期

基金：

俄罗斯基础研究基金会;

关键词：

ELECTRON-SPIN-RESONANCE; TRANSFORMATIONS; MOLECULES; DENSITY; ETHER;

D O I：

10.1134/S0018143909040110

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

It was shown that trimethylene oxide (oxetane) radical cations were converted at 77 K into either distonic radical cations center dot CH(2)CH(2)CH=OH(+) or 2-oxetanyl radicals, depending on the freonic matrix used, by the action of light at lambda = 546 nm and trimethylene sulfide radical cations transformed into distonic radical cations CH(2)CHSH(+)CH (2) (center dot) under 436-nm irradiation. The quantum yields of the photochemical reactions were determined. Quantum-chemical calculations on the structure and HFC constants of the radical cations and possible paramagnetic products of their transformation were performed. The reasons behind the observed difference in reactivity between the radical cations under the action of light are discussed.

引用

页码：303 / 311

页数：9

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