title: Quantitative catalyst-substrate association relationships between metathesis molybdenum or ruthenium carbene complexes and their substrates.
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.
authors.affiliation: Center for Time-Resolved Diffraction, Department of Chemistry, Graduate School of Nanoscience & Technology (WCU), KAIST, Daejeon, Korea.
authors.forename: Kyung Hwan
authors.initials: KH
authors.lastname: Kim
authors.forename: Taedong
authors.initials: T
authors.lastname: Ok
authors.forename: Kwangyeol
authors.initials: K
authors.lastname: Lee
authors.forename: Hee-Seung
authors.initials: HS
authors.lastname: Lee
authors.forename: Kyu Tae
authors.initials: KT
authors.lastname: Chang
authors.forename: Hyotcherl
authors.initials: H
authors.lastname: Ihee
authors.forename: Jeong-Hun
authors.initials: JH
authors.lastname: Sohn
mesh_terms: 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
chemical_list: D000466:Alkadienes; D000475:Alkenes; D000480:Alkynes; D009942:Organometallic Compounds; C030011:carbene; D012428:Ruthenium; D008982:Molybdenum; D008697:Methane