• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Gas Phase Generation of HCCCS and CCCHS Radicals from Anionic Precursors. The Rearrangement of CCCHS to HCCCS. A Joint Experimental and Theoretical Study
【24h】

Gas Phase Generation of HCCCS and CCCHS Radicals from Anionic Precursors. The Rearrangement of CCCHS to HCCCS. A Joint Experimental and Theoretical Study

机译：由阴离子前体气相生成HCCCS和CCCHS自由基。从CCCHS到HCCCS的重新安排。联合实验和理论研究

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

Theoretical studies at the CCSD(T)/aug-cc-pVDZ//B3LYP/aug-cc-p VDZ level of theory indicate that there are four stable radicals with CCC bond connectivity on the C_3HS potential surface, namely, HCCCS, CCHCS, CCCHS, and (cyclo-C_3H)=S. Of these structures, two have been synthesized by one electron vertical oxidation of precursor anions, formed as follows: (i) CH_3-C≡C-S-C_2H_5 + O~(-·) → (HCCCS)~- + H_2O + C_2H_5~· and (ii) Me_3Si-C≡C-CH(cyclo-SCH_2CH_2S) + F~- → ~-C≡C-CH=S = Me_3SiF + cyclo-SC_2H_4. A comparison of the ~-CR~+ and ~-NR~+ spectra of these two anions indicate that the neutral HCCCS is stable with a lifetime of at least 1 μs, whereas the oxidation of (CCCHS)~- leads to two neutrals, CCCHS and HCCCS. Theoretical calculations indicate that the rearrangement of CCCHS to HCCCS can occur by three pathways; concerted H or S rearrangements or the stepwise H rearrangement process CCCCHS → CCHCS → (cyclo-C_3H) = S → HCCCS. Comparison of the ~-CR~+ and ~-NR~+ spectra of (CC~(13)CHS)~- indicates that at least a part of the rearrangement involves the S migration pathway. Theoretical considerations suggest that H rearrangement should compete with S rearrangement: there is no experimental evidence to confirm or refute this proposal.
机译：在CCSD（T）/ aug-cc-pVDZ // B3LYP / aug-cc-p VDZ理论水平上的理论研究表明，C_3HS势能面上有四个具有CCC键连接性的稳定基团，即HCCCS，CCCHS， CCCHS，并且（cyclo-C_3H）= S。在这些结构中，通过前体阴离子的一次电子垂直氧化合成了两种结构，结构如下：（i）CH_3-C≡CS-C_2H_5+ O〜（-·）→（HCCCS）〜-+ H_2O + C_2H_5〜· （ii）Me_3Si-C≡C-CH（环-SCH_2CH_2S）+ F-→→-C≡C-CH= S = Me_3SiF +环SC_2H_4。这两种阴离子的〜-CR〜+和〜-NR〜+光谱比较表明，中性HCCCS是稳定的，寿命至少为1μs，而（CCCHS）〜-的氧化会导致两个中性， CCCHS和HCCCS。理论计算表明，CCCHS向HCCCS的重排可通过三种途径发生。一致的H或S重排或逐步的H重排过程CCCCHS→CCHCS→（cyclo-C_3H）= S→HCCCS。 （CC〜（13）CHS）~~的〜-CR〜+和〜-NR〜+光谱的比较表明，至少部分重排涉及S迁移途径。理论上的考虑表明，H重排应该与S重排竞争：没有实验证据可以证实或反驳这一提议。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号