Relative reaction rates of olefin substrates with ruthenium(II) carbene metathesis initiators
Relative reaction rates of olefin substrates with ruthenium(II) carbene metathesis initiators
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DOI：
10.1021/om9710172
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发表时间：
1998-06-08
期刊：
影响因子：
2.8
通讯作者：
Grubbs, RH
中科院分区：
文献类型：
--
作者：
Ulman, M;Grubbs, RH
研究了不同空间位阻、不同几何构型以及不同电子结构对位取代苯乙烯的端烯烃在反式-（PCy 3）（2）Cl 2 Ru = CHR复分解引发剂作用下的复分解反应，发现大体积烯烃的反应速度较慢，反式内烯烃的反应速度比顺式慢.发现所有反应的动力学产物都是亚烷基而不是亚甲基。观察到的效果被用来解释开环交叉复分解的机制。没有观察到线性电子效应。
The metathesis of terminal olefins having different steric bulk and different geometries as well as electronically different para-substituted styrenes was studied with the ruthenium-based metathesis initiators trans-(PCy3)(2)Cl2Ru=CHR. Bulkier olefins were found to react slower, and trans internal olefins were found to be slower than cis. The kinetic product of all reactions was found to be the alkylidene rather than the methylidene. Observed effects were used to explain the mechanism of ring-opening cross metathesis. No linear electronic effects were observed.