Mechanism of the Reaction of Vinyl Chloride with (α-diimine)PdMe+ Species
Organometallics2010Vol. 29(7), pp. 1750–1760
Citations Over TimeTop 21% of 2010 papers
Abstract
The reaction of vinyl chloride (VC) with (α-diimine)PdMe+ species yields (α-diimine)PdCl(propene)+. Isotope labeling experiments using the deuterium-labeled vinyl chlorides 1-VC-d1 and Z-VC-d1 combined with DFT computations establish that this reaction proceeds by 2,1-insertion of VC to produce β-H agostic (α-diimine)Pd(CHClCH2Me)+, chain-walking isomerization to generate β-Cl dative (α-diimine)Pd(CHMeCH2Cl)+, and syn β-Cl elimination. The labeling experiments rule out mechanisms involving initial 1,2-insertion or C−Cl oxidative addition. The computational results and the observation of small amounts of propene-d2 argue against mechanisms involving 2,1-insertion followed by α-Cl elimination and a 1,2 H-shift.
Related Papers
- → Aromatic vs Aliphatic C−H Bond Activation by Rhodium(I) as a Function of Agostic Interactions: Catalytic H/D Exchange between Olefins and Methanol or Water(2003)118 cited
- → Origin of Regiochemical Control in Rh(III)/Rh(V)-Catalyzed Reactions of Unsaturated Oximes and Alkenes to Form Pyrdines(2019)57 cited
- → HCo(CO)3-Catalyzed Propene Hydroformylation. Insight into Detailed Mechanism(2003)59 cited
- → Intrinsic Aptitude of Cationic Methyl- and Ethylpalladium To Associate Ethylene and To Further Undergo Subsequent Migratory Insertion. A Theoretical Study(1996)36 cited
- → Oxidative addition, reductive elemination, and isomerization reactions of organoplatinum complexes(1974)59 cited