Mechanism of the Reaction of Vinyl Chloride with (α-diimine)PdMe+ Species

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• 作者：Stefan M. Kilyanek ; Edward J. Stoebenau ; III ; Nawaporn Vinayavekhin ; Richard F. Jordan
• 刊名：Organometallics
• 出版年：2010
• 出版时间：April 12, 2010
• 年：2010
• 卷：29
• 期：7
• 页码：1750-1760
• 全文大小：1085K
• 年卷期：v.29,no.7(April 12, 2010)
• ISSN：1520-6041

文摘

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.