三重组 1,3-二烯利烯 (Ph-C-C-C-Ph) 的三重组
Jeffrey T DePinto1, Wendy A deProphetis, Jessica L Menke
1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706-1396, USA.
Journal of the American Chemical Society
|February 7, 2007
概括
1,3-二乙烯二烯的光解产生三重组1,3-二乙烯二烯,一个1,3-烯二基. 这种二基基经过光化学循环转化为二环烯,证明了可逆的碳化合物化学反应.
科学领域:
- 摄影化学的使用.
- 有机化学 有机化学
- 频谱学是一种光谱学.
背景情况:
- 碳是有机合成中至关重要的反应性中间体.
- 了解艾伦基碳的结构和反应性是推动碳化学进步的关键.
- 1,3-二二二烯作为产生特定碳烯物种的前体.
研究的目的:
- 为了描述光化学生成的三重体1,3-二 propynylidene.
- 为了研究这个艾伦基基的结构异构体和平衡几何学.
- 为了探索三重体1,3-二烯利丁的光化学反应性和捕获行为.
主要方法:
- 在低温矩阵中对1,3-二二二烯的光解.
- 使用IR,UV/vis和EPR光谱学的光谱表征.
- 密度函数理论 (DFT) 的计算.
- 用分子氧 (O2) 进行化学捕获实验.
主要成果:
- 产生的和特征的三重体1,3-二烯利丁,存在于两个可区分的形状异构体.
- 均衡几何学被确定为一个高度对称的D2d艾伦基二基,而不是一种键位定位的乙基碳酸.
- 化学捕获产生了碳氧化物,和二氧化,这是典型的碳捕获产品.
- 光化学辐射导致可逆循环转化为单片二环烯.
结论:
- 三重体1,3-二烯利基采用一个全基二基结构.
- 它的光化学行为包括循环转化为二cyclopropenylidene,展示可逆的碳转化.
- 这项研究提供了对艾伦基二根基的结构,光谱和反应性的洞察.
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