AI Article Synopsis
- The study used IR spectroscopy to analyze the kinetics of enyne metathesis involving different alkyne and alkene pairs.
- It was found that more substituted alkynes increase the rate of the metathesis reaction, and interactions like chelation with propargylic esters were not a factor based on comparisons to hydrocarbon alkynes.
- The results suggest a reaction mechanism that starts with alkylidene, involving specific resting states of phosphine-bound ruthenium carbene and the rate-limiting steps concerning vinyl carbene intermediates in reactions with alkyne-1-hexene.
Article Abstract
The kinetics of enyne metathesis were studied by IR spectroscopy for a variety of alkyne-alkene combinations. The rate law was determined for alkyne-ethylene and alkyne-1-hexene cross metathesis. In the cases examined, greater substitution on the alkyne accelerates the rate of metathesis, and chelation by propargylic esters was ruled out through rate comparison with hydrocarbon alkynes. The findings are discussed in terms of an alkylidene-first reaction mechanism, phosphine-bound ruthenium carbene resting states, and the rate-determining turnover of vinyl carbene intermediates (for alkyne-1-hexene metatheses).
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| http://dx.doi.org/10.1021/ja050174m | DOI Listing |
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