三重体1,3-二甲基烯 (MeC3Me) 的光谱和光化学
Stephanie N Knezz1, Terese A Waltz1, Benjamin C Haenni1
1Department of Chemistry, University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706-1322, United States.
Journal of the American Chemical Society
|September 20, 2016
概括
通过2 - - 3 - 的光解产生三重体1,3 - 甲基利. 这种碳具有轴对称性,并且与其母体C3H2系统不同,容易经历迁移.
科学领域:
- 摄影化学
- 光谱学
- 量子化学
背景情况:
- 在有机化学中,非局部化的碳链和碳素是基本的.
- 对于反应设计来说,了解替代剂对碳化合物特性的影响至关重要.
- 主C3H2系统表现出丰富的光化学,作为一个基准.
研究的目的:
- 用光谱鉴定三重体1,3-二甲基化 (MeC3Me).
- 研究甲基替代剂对非局部化碳链的影响.
- 将MeC3Me的光化学与母C3H2进行比较.
主要方法:
- 在低温基质中对2-diazo-3-pentyne进行光解.
- 频谱表征:红外 (IR),电子吸收和电子磁共振 (EPR).
- 量子化学计算 (CCSD) /ANO1).
主要成果:
- 三重体MeC3Me的光谱特征显示出一个近线,轴对称的结构.
- EPR光谱产生了与轴对称相一致的零场分裂参数.
- 由于甲基替代剂,理论分析表明了显著的旋转极化.
- 在紫外线照射时,MeC3Me经历了1,2-迁移,形成了pent-1-en-3-yne.
结论:
- 脱位卡链上的甲基替代物会影响电子结构和反应性.
- 与母体C3H2相比,三元体MeC3Me表现出不同的光化学行为.
- 容易的迁移途径限制了MeC3Me的其他光异构化可能性.
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