Premium
The Effect of Chloride Ions on the Mechanism of the Oxidative Addition of Cyclic Allylic Carbonates to Pd 0 Complexes by Formation of Neutral[(η 1 ‐allyl)PdClL 2 ] Complexes
Author(s) -
Cantat Thibault,
Agenet Nicolas,
Jutand Anny,
Pleixats Roser,
MorenoMañas Marcial
Publication year - 2005
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200500345
Subject(s) - chemistry , allylic rearrangement , isomerization , cationic polymerization , oxidative addition , medicinal chemistry , chloride , chloroform , cis–trans isomerism , ion , stereochemistry , catalysis , polymer chemistry , organic chemistry
The reversible oxidative addition of a cyclic allylic carbonate cis ‐ 1 to palladium(0) complexes ligated by PPh 3 is affected by chloride ions in DMF or chloroform. In the presence of chloride ions, the oxidative addition may become irreversible and the rate of isomerization of cis ‐ 1 to trans ‐ 1 is slowed down. This is a consequence of a slower isomerization of the cationic complex [(η 3 ‐allyl)Pd(PPh 3 ) 2 ] + ( cis ‐ 2 + ) to trans ‐ 2 + due to the formation of neutral [(η 1 ‐allyl)PdCl(PPh 3 ) 2 ] ( cis ‐ 3 / trans ‐3 ) complexes. Such complexes are formed instead of the cationic cis ‐ 2 + and trans ‐ 2 + whatever the source of chloride ions, i.e., whether voluntarily added to the cationic complexes cis ‐ 2 + and trans ‐ 2 + , voluntarily added in the oxidative addition of cis ‐ 1 with Pd 0 complexes ligated to PPh 3 , or introduced in the dimeric complexes [(η 3 ‐allyl)Pd(μ‐Cl)] 2 ( cis‐ 5 / trans ‐ 5 ). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)