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Quantitative Catalyst-Substrate Association Relationships between Metathesis Molybdenum or Ruthenium Carbene Complexes and Their Substrates
- Authors
- Kim, Kyung Hwan; Ok, Taedong; Lee, Kwangyeol; Lee, Hee-Seung; Chang, Kyu Tae; Ihee, Hyotcherl; Sohn, Jeong-Hun
- Issue Date
- 1-9월-2010
- Publisher
- AMER CHEMICAL SOC
- Citation
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.132, no.34, pp.12027 - 12033
- Indexed
- SCIE
SCOPUS
- Journal Title
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
- Volume
- 132
- Number
- 34
- Start Page
- 12027
- End Page
- 12033
- ISSN
- 0002-7863
- Abstract
- 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.
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