Quantitative Catalyst−Substrate Association Relationships between Metathesis Molybdenum or Ruthenium Carbene Complexes and Their Substrates
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- 作者：Kyung Hwan Kim ; Taedong Ok ; Kwangyeol Lee ; Hee-Seung Lee ; Kyu Tae Chang ; Hyotcherl Ihee ; Jeong-Hun Sohn
- 刊名：Journal of the American Chemical Society
- 出版年：2010
- 出版时间：September 1, 2010
- 年：2010
- 卷：132
- 期：34
- 页码：12027-12033
- 全文大小：358K
- 年卷期：v.132,no.34(September 1, 2010)
- ISSN：1520-5126
文摘
Herein we present the long-sought quantitative catalyst−substrate association relationships based on experimentally measured quantitative association preferences of diverse metathesis Mo and Ru catalysts (Mo-1, Schrock Mo; Mo-2, Schrock−Hoveyda Mo; Ru-1, Grubbs first generation Ru; Ru-2, Grubbs second generation Ru; Ru-3:, Grubbs−Hoveyda first generation Ru; and Ru-4, Grubbs−Hoveyda second generation Ru) to their substrates (alkenes, alkynes and allenes), determined directly by a general method based on FRET principle. The determined substrate preferences are proved to be dependent on the molecular identity of the catalyst, exhibiting the preference order of alkyne > alkene > allene for Mo-1 and Mo-2, allene > alkene > alkyne for Ru-1 and Ru-3, and alkyne > allene > alkene for Ru-2 and Ru-4. The results enable us to probe metathesis mechanisms by answering issues in metathesis reactions including the controversial reaction initiation in enyne or allenyne metathesis.