Quantitative catalyst-substrate association relationships between metathesis molybdenum or ruthenium carbene complexes and their substrates.
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.
Kim
Kyung Hwan
KH
Center for Time-Resolved Diffraction, Department of Chemistry, Graduate School of Nanoscience & Technology (WCU), KAIST, Daejeon, Korea.
Ok
Taedong
T
Lee
Kwangyeol
K
Lee
Hee-Seung
HS
Chang
Kyu Tae
KT
Ihee
Hyotcherl
H
Sohn
Jeong-Hun
JH
D000466:Alkadienes / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry; D000480:Alkynes / Q000737:chemistry; D002384:Catalysis; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
D000466:Alkadienes; D000475:Alkenes; D000480:Alkynes; D009942:Organometallic Compounds; C030011:carbene; D012428:Ruthenium; D008982:Molybdenum; D008697:Methane