Kinetic data on the synergetic role of amines and water in the reduction of phosphine-ligated palladium(II) to palladium(0)

Christian Amatore; Laurent El Kaïm; Laurence Grimaud; Anny Jutand; Alice Meignié; Georgy Romanov

doi:10.1002/ejoc.201402519

Kinetic data on the synergetic role of amines and water in the reduction of phosphine-ligated palladium(II) to palladium(0)

Christian Amatore
, Laurent El Kaïm
, Laurence Grimaud
, Anny Jutand
, Alice Meignié
, Georgy Romanov

Centre national de la recherche scientifique
Laboratoire de Synthèse Organique

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

32 Citations (Scopus)

Abstract

Tertiary amines such as EtN(iPr)₂ do not reduce [PdCl ₂(PPh₃)₂] into a Pd⁰ complex. The latter is formed only after the addition of water (generation of HO ^-), as was reported by Grushin and Alper for NEt₃. The mechanism of the Pd^II/Pd⁰ reduction performed in the presence of an excess amount of PPh₃ is established quantitatively by means of electrochemical techniques that provide kinetic data (determination of the equilibrium and rate constants) for the disappearance of [PdCl ₂(PPh₃)₂] and the formation of [Pd ⁰(PPh₃)₃]. [PdCl(OH)(PPh₃) ₂] is formed, which allows reductive elimination between OH and the ligated PPh₃ (zero-order reaction for PPh₃), and this leads to a Pd⁰ complex. The reducing agent is ligated PPh ₃, which ultimately yields (O)PPh₃. The rate of the overall reduction process is controlled by the amount of water that imposes the concentration of HO^-.

Original language	English
Pages (from-to)	4709-4713
Number of pages	5
Journal	European Journal of Organic Chemistry
Volume	2014
Issue number	22
DOIs	https://doi.org/10.1002/ejoc.201402519
Publication status	Published - 1 Jan 2014
Externally published	Yes

Keywords

Amines
Palladium
Phosphanes
Reaction mechanisms
Reduction
Water chemistry

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10.1002/ejoc.201402519

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title = "Kinetic data on the synergetic role of amines and water in the reduction of phosphine-ligated palladium(II) to palladium(0)",

abstract = "Tertiary amines such as EtN(iPr)2 do not reduce [PdCl 2(PPh3)2] into a Pd0 complex. The latter is formed only after the addition of water (generation of HO -), as was reported by Grushin and Alper for NEt3. The mechanism of the PdII/Pd0 reduction performed in the presence of an excess amount of PPh3 is established quantitatively by means of electrochemical techniques that provide kinetic data (determination of the equilibrium and rate constants) for the disappearance of [PdCl 2(PPh3)2] and the formation of [Pd 0(PPh3)3]. [PdCl(OH)(PPh3) 2] is formed, which allows reductive elimination between OH and the ligated PPh3 (zero-order reaction for PPh3), and this leads to a Pd0 complex. The reducing agent is ligated PPh 3, which ultimately yields (O)PPh3. The rate of the overall reduction process is controlled by the amount of water that imposes the concentration of HO-.",

keywords = "Amines, Palladium, Phosphanes, Reaction mechanisms, Reduction, Water chemistry",

author = "Christian Amatore and \{El Ka{\"i}m\}, Laurent and Laurence Grimaud and Anny Jutand and Alice Meigni{\'e} and Georgy Romanov",

year = "2014",

month = jan,

day = "1",

doi = "10.1002/ejoc.201402519",

language = "English",

volume = "2014",

pages = "4709--4713",

journal = "European Journal of Organic Chemistry",

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TY - JOUR

T1 - Kinetic data on the synergetic role of amines and water in the reduction of phosphine-ligated palladium(II) to palladium(0)

AU - Amatore, Christian

AU - El Kaïm, Laurent

AU - Grimaud, Laurence

AU - Jutand, Anny

AU - Meignié, Alice

AU - Romanov, Georgy

PY - 2014/1/1

Y1 - 2014/1/1

N2 - Tertiary amines such as EtN(iPr)2 do not reduce [PdCl 2(PPh3)2] into a Pd0 complex. The latter is formed only after the addition of water (generation of HO -), as was reported by Grushin and Alper for NEt3. The mechanism of the PdII/Pd0 reduction performed in the presence of an excess amount of PPh3 is established quantitatively by means of electrochemical techniques that provide kinetic data (determination of the equilibrium and rate constants) for the disappearance of [PdCl 2(PPh3)2] and the formation of [Pd 0(PPh3)3]. [PdCl(OH)(PPh3) 2] is formed, which allows reductive elimination between OH and the ligated PPh3 (zero-order reaction for PPh3), and this leads to a Pd0 complex. The reducing agent is ligated PPh 3, which ultimately yields (O)PPh3. The rate of the overall reduction process is controlled by the amount of water that imposes the concentration of HO-.

AB - Tertiary amines such as EtN(iPr)2 do not reduce [PdCl 2(PPh3)2] into a Pd0 complex. The latter is formed only after the addition of water (generation of HO -), as was reported by Grushin and Alper for NEt3. The mechanism of the PdII/Pd0 reduction performed in the presence of an excess amount of PPh3 is established quantitatively by means of electrochemical techniques that provide kinetic data (determination of the equilibrium and rate constants) for the disappearance of [PdCl 2(PPh3)2] and the formation of [Pd 0(PPh3)3]. [PdCl(OH)(PPh3) 2] is formed, which allows reductive elimination between OH and the ligated PPh3 (zero-order reaction for PPh3), and this leads to a Pd0 complex. The reducing agent is ligated PPh 3, which ultimately yields (O)PPh3. The rate of the overall reduction process is controlled by the amount of water that imposes the concentration of HO-.

KW - Amines

KW - Palladium

KW - Phosphanes

KW - Reaction mechanisms

KW - Reduction

KW - Water chemistry

U2 - 10.1002/ejoc.201402519

DO - 10.1002/ejoc.201402519

M3 - Article

AN - SCOPUS:84904740230

SN - 1434-193X

VL - 2014

SP - 4709

EP - 4713

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 22

ER -

Kinetic data on the synergetic role of amines and water in the reduction of phosphine-ligated palladium(II) to palladium(0)

Abstract

Keywords

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