Electric Literature of 32993-05-8, Chemistry can be defined as the study of matter and the changes it undergoes. You¡¯ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a patent, introducing its new discovery.
Ruthenium-catalyzed hydration of 1-alkynes to give aldehydes: Insight into anti-Markovnikov regiochemistry
The mechanism of the selective conversion of 1-alkynes to aldehydes by hydration was investigated by isolating organic and organometallic byproducts, deuterium-labeling experiments, and DFT calculations. The D-labeled acetylenic hydrogen of 1-alkyne was found exclusively in the formyl group of the resulting aldehydes. After the reaction, the presence of metal-coordinated CO was confirmed. All of the experimental results strongly suggest the involvement of a metal-acyl intermediate with the original acetylenic hydrogen also bound to the metal center as a hydride, with the next step being release of aldehyde by reductive elimination. Theoretical analyses suggest that the first step of the catalytic cycle is not oxidative addition of acetylene C-H or tautomerization of eta2-alkyne to a vinylidene complex, but rather protonation of the coordinated 1-alkyne at the substituted carbon to form a metal-vinyl intermediate. This cationic intermediate then isomerizes to Ru(IV)-hydride-vinylidene via alpha-hydride migration of the vinyl group to the metal center, followed by attack of the vinylidene alpha-carbon by OH- to give the metal-hydride-acyl intermediate.
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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI