title: From Resting State to the Steady State: Mechanistic Studies of Ene-Yne Metathesis Promoted by the Hoveyda Complex.
abstract: The kinetics of intermolecular ene-yne metathesis (EYM) with the Hoveyda precatalyst (Ru1) has been studied. For 1-hexene metathesis with 2-benzoyloxy-3-butyne, the experimental rate law was determined to be first-order in 1-hexene (0.3-4 M), first-order in initial catalyst concentration, and zero-order for the terminal alkyne. At low catalyst concentrations (0.1 mM), the rate of precatalyst initiation was observed by UV-vis and the alkyne disappearance was observed by in situ FT-IR. Comparison of the rate of precatalyst initiation and the rate of EYM shows that a low, steady-state concentration of active catalyst is rapidly produced. Application of steady-state conditions to the carbene intermediates provided a rate treatment that fit the experimental rate law. Starting from a ruthenium alkylidene complex, competition between 2-isopropoxystyrene and 1-hexene gave a mixture of 2-isopropoxyarylidene and pentylidene species, which were trappable by the Buchner reaction. By varying the relative concentration of these alkenes, 2-isopropoxystyrene was found to be 80 times more effective than 1-hexene in production of their respective Ru complexes. Buchner-trapping of the initiation of Ru1 with excess 1-hexene after 50% loss of Ru1 gave 99% of the Buchner-trapping product derived from precatalyst Ru1. For the initiation process, this shows that there is an alkene-dependent loss of precatalyst Ru1, but this does not directly produce the active catalyst. A faster initiating precatalyst for alkene metathesis gave similar rates of EYM. Buchner-trapping of ene-yne metathesis failed to deliver any products derived from Buchner insertion, consistent with rapid decomposition of carbene intermediates under ene-yne conditions. An internal alkyne, 1,4-diacetoxy-2-butyne, was found to obey a different rate law. Finally, the second-order rate constant for ene-yne metathesis was compared to that previously determined by the Grubbs second-generation carbene complex: Ru1 was found to promote ene-yne metathesis 62 times faster at the same initial precatalyst concentration.
authors.affiliation: Department of Chemistry, University at Buffalo, the State University of New York , Buffalo, New York 14260-3000, United States.
authors.forename: Justin R
authors.initials: JR
authors.lastname: Griffiths
authors.affiliation: Department of Chemistry, University at Buffalo, the State University of New York , Buffalo, New York 14260-3000, United States.
authors.forename: Jerome B
authors.initials: JB
authors.lastname: Keister
authors.affiliation: Department of Chemistry, University at Buffalo, the State University of New York , Buffalo, New York 14260-3000, United States.
authors.forename: Steven T
authors.initials: ST
authors.lastname: Diver