Formation of anionic palladium(0) complexes ligated by the trifluoroacetate ion and their reactivity in oxidative addition

Christian Amatore; Anny Jutand; Frédéric Lemaître; Jean Luc Ricard; Sebastian Kozuch; Sason Shaik

doi:10.1016/j.jorganchem.2004.05.012

Formation of anionic palladium(0) complexes ligated by the trifluoroacetate ion and their reactivity in oxidative addition

Christian Amatore^*, Anny Jutand, Frédéric Lemaître, Jean Luc Ricard, Sebastian Kozuch, Sason Shaik

^*Corresponding author for this work

Institute of Chemistry

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

56 Scopus citations

Abstract

As established previously for Pd(OAc)₂, Pd⁰ complexes are formed in situ from Pd(OCOCF₃)₂ and n equiv. triarylphosphines (4-Z-C₆H₄)₃P (Z = CF ₃, F, Cl, H, CH₃; n ≥ 3). The phosphines are the intramolecular reducing agents and are oxidized to triarylphosphine oxides. The generated Pd⁰ complexes are anionic species ligated by the trifluoroacetate anion: Pd⁰(PAr₃)_n(OCOCF ₃)^- (n = 2 or 3). Pd⁰(PAr₃) ₂(OCOCF₃)^- is the reactive species involved in the oxidative addition to PhI. This leads to trans-PhPd(OCOCF ₃)(PPh₃)₂, involved in equilibrium with the cationic complex trans-[PhPd(PPh₃)₂(DMF)]⁺, instead of the expected trans-PhPdI(PPh₃)₂ complex. The existence of anionic Pd⁰ complexes ligated by the acetate or trifluoroacetate ions delivered by the precursors Pd(OAc)₂ or Pd(OCOCF₃)₂, respectively, as well as their comparative reactivity in oxidative additions are consistent with theoretical DFT calculations.

Original language	English
Pages (from-to)	3728-3734
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	689
Issue number	23
DOIs	https://doi.org/10.1016/j.jorganchem.2004.05.012
State	Published - 15 Nov 2004

Keywords

Acetate
Kinetics
Mechanism
Oxidative addition
Palladium
Trifluoroacetate

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10.1016/j.jorganchem.2004.05.012

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title = "Formation of anionic palladium(0) complexes ligated by the trifluoroacetate ion and their reactivity in oxidative addition",

abstract = "As established previously for Pd(OAc)2, Pd0 complexes are formed in situ from Pd(OCOCF3)2 and n equiv. triarylphosphines (4-Z-C6H4)3P (Z = CF 3, F, Cl, H, CH3; n ≥ 3). The phosphines are the intramolecular reducing agents and are oxidized to triarylphosphine oxides. The generated Pd0 complexes are anionic species ligated by the trifluoroacetate anion: Pd0(PAr3)n(OCOCF 3)- (n = 2 or 3). Pd0(PAr3) 2(OCOCF3)- is the reactive species involved in the oxidative addition to PhI. This leads to trans-PhPd(OCOCF 3)(PPh3)2, involved in equilibrium with the cationic complex trans-[PhPd(PPh3)2(DMF)]+, instead of the expected trans-PhPdI(PPh3)2 complex. The existence of anionic Pd0 complexes ligated by the acetate or trifluoroacetate ions delivered by the precursors Pd(OAc)2 or Pd(OCOCF3)2, respectively, as well as their comparative reactivity in oxidative additions are consistent with theoretical DFT calculations.",

keywords = "Acetate, Kinetics, Mechanism, Oxidative addition, Palladium, Trifluoroacetate",

author = "Christian Amatore and Anny Jutand and Fr{\'e}d{\'e}ric Lema{\^i}tre and Ricard, {Jean Luc} and Sebastian Kozuch and Sason Shaik",

year = "2004",

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day = "15",

doi = "10.1016/j.jorganchem.2004.05.012",

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T1 - Formation of anionic palladium(0) complexes ligated by the trifluoroacetate ion and their reactivity in oxidative addition

AU - Amatore, Christian

AU - Jutand, Anny

AU - Lemaître, Frédéric

AU - Ricard, Jean Luc

AU - Kozuch, Sebastian

AU - Shaik, Sason

PY - 2004/11/15

Y1 - 2004/11/15

N2 - As established previously for Pd(OAc)2, Pd0 complexes are formed in situ from Pd(OCOCF3)2 and n equiv. triarylphosphines (4-Z-C6H4)3P (Z = CF 3, F, Cl, H, CH3; n ≥ 3). The phosphines are the intramolecular reducing agents and are oxidized to triarylphosphine oxides. The generated Pd0 complexes are anionic species ligated by the trifluoroacetate anion: Pd0(PAr3)n(OCOCF 3)- (n = 2 or 3). Pd0(PAr3) 2(OCOCF3)- is the reactive species involved in the oxidative addition to PhI. This leads to trans-PhPd(OCOCF 3)(PPh3)2, involved in equilibrium with the cationic complex trans-[PhPd(PPh3)2(DMF)]+, instead of the expected trans-PhPdI(PPh3)2 complex. The existence of anionic Pd0 complexes ligated by the acetate or trifluoroacetate ions delivered by the precursors Pd(OAc)2 or Pd(OCOCF3)2, respectively, as well as their comparative reactivity in oxidative additions are consistent with theoretical DFT calculations.

AB - As established previously for Pd(OAc)2, Pd0 complexes are formed in situ from Pd(OCOCF3)2 and n equiv. triarylphosphines (4-Z-C6H4)3P (Z = CF 3, F, Cl, H, CH3; n ≥ 3). The phosphines are the intramolecular reducing agents and are oxidized to triarylphosphine oxides. The generated Pd0 complexes are anionic species ligated by the trifluoroacetate anion: Pd0(PAr3)n(OCOCF 3)- (n = 2 or 3). Pd0(PAr3) 2(OCOCF3)- is the reactive species involved in the oxidative addition to PhI. This leads to trans-PhPd(OCOCF 3)(PPh3)2, involved in equilibrium with the cationic complex trans-[PhPd(PPh3)2(DMF)]+, instead of the expected trans-PhPdI(PPh3)2 complex. The existence of anionic Pd0 complexes ligated by the acetate or trifluoroacetate ions delivered by the precursors Pd(OAc)2 or Pd(OCOCF3)2, respectively, as well as their comparative reactivity in oxidative additions are consistent with theoretical DFT calculations.

KW - Acetate

KW - Kinetics

KW - Mechanism

KW - Oxidative addition

KW - Palladium

KW - Trifluoroacetate

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ER -

Formation of anionic palladium(0) complexes ligated by the trifluoroacetate ion and their reactivity in oxidative addition

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