1047665-07-5Relevant academic research and scientific papers
Mechanistic and kinetic investigation on the formation of palladacyclopentadiene complexes. A novel interpretation involving a bimolecular self-reaction of a monoalkyne intermediate
Holuigue,Ernsting,Visentin,Levi,Canovese,Elsevier
, p. 4050 - 4055 (2009/02/06)
The stoichiometric reaction between the complex [Pd(η2dmfu) (BiPy)] (dmfu = dimethylfumarate; BiPy = 2,2′-bipyridine) and the deactivated alkynes dmbd (dimethyl-2-butynedioate) and pna (methyl (4-nitrophenyl)propynoate), providing the respective palladacyclopentadienes, was investigated. The mechanism leading to the palladacyclopentadiene derivative involves a bimolecular self-rearrangement of the monoalkyne intermediate [Pd(η2-alk)(BiPy)] (alk = dmbd, pna), followed by the customary attack of the free alkyne on the intermediate [Pd(η2-alk)(BiPy)] itself and on the elusive and highly reactive naked palladium [Pd(BiPy)(0)] formed. The alkyne pna proved to be less effective in the displacement of dmfu than dmbd. The reaction under stoichiometric equimolar conditions of the latter with [Pd(η2-dmfu)(BiPy)] allows the direct determination of the bimolecular self-reaction rate constant k c and consequently the assessment of all the rate constants involved in the overall mechanistic network.
