The effect of chloride ions on the mechanism of the oxidative addition of cyclic allylic carbonates to Pd0 complexes by formation of neutral [(η1-allyl)PdClL<inf>2</inf>] complexes

Thibault Cantat; Nicolas Agenet; Anny Jutand; Roser Pleixats; Marcial Moreno-Mañas

doi:10.1002/ejoc.200500345

The effect of chloride ions on the mechanism of the oxidative addition of cyclic allylic carbonates to Pd0 complexes by formation of neutral [(η1-allyl)PdClL<inf>2</inf>] complexes

Thibault Cantat, Nicolas Agenet, Anny Jutand, Roser Pleixats, Marcial Moreno-Mañas

Department of Chemistry

Research output: Contribution to journal › Article › Research › peer-review

19 Citations (Scopus)

Abstract

The reversible oxidative addition of a cyclic allylic carbonate cis-1 to palladium(0) complexes ligated by PPh3 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 [(η3-allyl)Pd(PPh3)2]+ (cis-2+) to trans-2+ due to the formation of neutral [(η1-allyl)PdCl(PPh3)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 PPh3, or introduced in the dimeric complexes [(η3-allyl)Pd(μ-Cl)]2 (cis-5/trans-5). © Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

Original language	English
Pages (from-to)	4277-4286
Journal	European Journal of Organic Chemistry
Issue number	20
DOIs	https://doi.org/10.1002/ejoc.200500345
Publication status	Published - 14 Oct 2005

Keywords

Allyl ligands
Carbonates
Halides
Palladium
Reaction mechanisms

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10.1002/ejoc.200500345

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Cantat, T., Agenet, N., Jutand, A., Pleixats, R., & Moreno-Mañas, M. (2005). The effect of chloride ions on the mechanism of the oxidative addition of cyclic allylic carbonates to Pd0 complexes by formation of neutral [(η1-allyl)PdClL<inf>2</inf>] complexes. European Journal of Organic Chemistry, (20), 4277-4286. https://doi.org/10.1002/ejoc.200500345

Cantat, Thibault ; Agenet, Nicolas ; Jutand, Anny ; Pleixats, Roser ; Moreno-Mañas, Marcial. / The effect of chloride ions on the mechanism of the oxidative addition of cyclic allylic carbonates to Pd0 complexes by formation of neutral [(η1-allyl)PdClL<inf>2</inf>] complexes. In: European Journal of Organic Chemistry. 2005 ; No. 20. pp. 4277-4286.

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title = "The effect of chloride ions on the mechanism of the oxidative addition of cyclic allylic carbonates to Pd0 complexes by formation of neutral [(η1-allyl)PdClL2] complexes",

abstract = "The reversible oxidative addition of a cyclic allylic carbonate cis-1 to palladium(0) complexes ligated by PPh3 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 [(η3-allyl)Pd(PPh3)2]+ (cis-2+) to trans-2+ due to the formation of neutral [(η1-allyl)PdCl(PPh3)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 PPh3, or introduced in the dimeric complexes [(η3-allyl)Pd(μ-Cl)]2 (cis-5/trans-5). {\textcopyright} Wiley-VCH Verlag GmbH & Co. KGaA, 2005.",

keywords = "Allyl ligands, Carbonates, Halides, Palladium, Reaction mechanisms",

author = "Thibault Cantat and Nicolas Agenet and Anny Jutand and Roser Pleixats and Marcial Moreno-Ma{\~n}as",

year = "2005",

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Cantat, T, Agenet, N, Jutand, A, Pleixats, R & Moreno-Mañas, M 2005, 'The effect of chloride ions on the mechanism of the oxidative addition of cyclic allylic carbonates to Pd0 complexes by formation of neutral [(η1-allyl)PdClL<inf>2</inf>] complexes', European Journal of Organic Chemistry, no. 20, pp. 4277-4286. https://doi.org/10.1002/ejoc.200500345

The effect of chloride ions on the mechanism of the oxidative addition of cyclic allylic carbonates to Pd0 complexes by formation of neutral [(η1-allyl)PdClL<inf>2</inf>] complexes. / Cantat, Thibault; Agenet, Nicolas; Jutand, Anny; Pleixats, Roser; Moreno-Mañas, Marcial.

In: European Journal of Organic Chemistry, No. 20, 14.10.2005, p. 4277-4286.

Research output: Contribution to journal › Article › Research › peer-review

TY - JOUR

T1 - The effect of chloride ions on the mechanism of the oxidative addition of cyclic allylic carbonates to Pd0 complexes by formation of neutral [(η1-allyl)PdClL2] complexes

AU - Cantat, Thibault

AU - Agenet, Nicolas

AU - Jutand, Anny

AU - Pleixats, Roser

AU - Moreno-Mañas, Marcial

PY - 2005/10/14

Y1 - 2005/10/14

N2 - The reversible oxidative addition of a cyclic allylic carbonate cis-1 to palladium(0) complexes ligated by PPh3 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 [(η3-allyl)Pd(PPh3)2]+ (cis-2+) to trans-2+ due to the formation of neutral [(η1-allyl)PdCl(PPh3)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 PPh3, or introduced in the dimeric complexes [(η3-allyl)Pd(μ-Cl)]2 (cis-5/trans-5). © Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

AB - The reversible oxidative addition of a cyclic allylic carbonate cis-1 to palladium(0) complexes ligated by PPh3 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 [(η3-allyl)Pd(PPh3)2]+ (cis-2+) to trans-2+ due to the formation of neutral [(η1-allyl)PdCl(PPh3)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 PPh3, or introduced in the dimeric complexes [(η3-allyl)Pd(μ-Cl)]2 (cis-5/trans-5). © Wiley-VCH Verlag GmbH & Co. KGaA, 2005.

KW - Allyl ligands

KW - Carbonates

KW - Halides

KW - Palladium

KW - Reaction mechanisms

U2 - 10.1002/ejoc.200500345

DO - 10.1002/ejoc.200500345

M3 - Article

SP - 4277

EP - 4286

IS - 20

ER -

The effect of chloride ions on the mechanism of the oxidative addition of cyclic allylic carbonates to Pd<sup>0</sup> complexes by formation of neutral [(η<sup>1</sup>-allyl)PdClL<inf>2</inf>] complexes

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Keywords

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