铜催化循环化中的离散桥梁和终端铜碳
Xuliang Dai1, Timothy H Warren
1Department of Chemistry, Georgetown University, Washington, DC. 20057, USA.
Journal of the American Chemical Society
|August 12, 2004
概括
铜(I) β-二甲基二胺酸复合物催化循环化反应. 一种二铜碳中间体被分离和特征,显示可逆解离到终端铜碳,有效地循环化 styrene.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 碳烯化学 碳烯化学
背景情况:
- 复合物中的铜 (I) 复合物与β-二甲基酸连接物是有效的催化剂.
- 碳转移反应在有机合成中至关重要.
研究的目的:
- 为了研究铜的催化活性(I) 在循环化中β-diketiminate复合物.
- 合成和描述新的二铜和终端铜碳物种.
主要方法:
- 用铜的催化 (I) β-二甲基二胺酸复合物.
- 二铜碳酸的隔离和结构特征.
- 碳反应的动力学研究.
- 密度函数理论 (DFT) 的计算.
主要成果:
- 复杂的铜 (I) 复合物 (Me2NN) 催化 styrene 环化.
- 一种双铜碳,[Me2NN]Cu]2(mu-CPh2),被分离出来并进行了结构特征.
- 这种双铜碳可逆地解离为终端铜碳,[Me2NN]Cu=CPh2.2.
- 终端铜碳有效地循环化 styrene 并分解为四乙烯.
- DFT研究表明,二铜碳化合物中 Cu-C pi 背接增强.
结论:
- 二铜碳中间体在铜催化循环化中起作用.
- 终端铜碳是可分离和反应性的物种.
- 连接物设计影响铜碳复合物的稳定性和反应性.
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