Conversion of Pd(I) off-cycle species into highly efficient cross-coupling catalysts.

Yaxu Liu; Vladislav A Voloshkin; Thomas Scattolin; Luigi Cavallo; Busra Dereli; Catherine S. J. Cazin; Steven P. Nolan

doi:10.1039/d1dt00929j

Conversion of Pd(I) off-cycle species into highly efficient cross-coupling catalysts.

Yaxu Liu, Vladislav A Voloshkin, Thomas Scattolin, Luigi Cavallo, Busra Dereli, Catherine S. J. Cazin, Steven P. Nolan

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

8 Scopus citations

Abstract

We report on the facile conversion of [Pd2(μ-Cl)(μ-η3-R-allyl)(NHC)2] complexes, which are commonly considered undesirable off-cycle species in cross-coupling reactions, into active [PdCl(μ-Cl)(NHC)]2 pre-catalysts. All reactions proceed under mild conditions (40 °C, 1-2 hours in acetone) using inexpensive HCl as both an oxidant and chloride source. DFT calculations were performed to explore the possible mechanism of this transformation, which appears to involve a combination of two different pathways. Moreover this study provides insights into factors favoring and hindering Pd(i) dimer formation undesirable in catalysis.

Original language	English (US)
Pages (from-to)	5420-5427
Number of pages	8
Journal	Dalton transactions (Cambridge, England : 2003)
Volume	50
Issue number	16
DOIs	https://doi.org/10.1039/d1dt00929j
State	Published - Apr 28 2021

ASJC Scopus subject areas

Inorganic Chemistry

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10.1039/d1dt00929j

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@article{f63a64cd9385469a80bb8b9cb8aaa15e,

title = "Conversion of Pd(I) off-cycle species into highly efficient cross-coupling catalysts.",

abstract = "We report on the facile conversion of [Pd2(μ-Cl)(μ-η3-R-allyl)(NHC)2] complexes, which are commonly considered undesirable off-cycle species in cross-coupling reactions, into active [PdCl(μ-Cl)(NHC)]2 pre-catalysts. All reactions proceed under mild conditions (40 °C, 1-2 hours in acetone) using inexpensive HCl as both an oxidant and chloride source. DFT calculations were performed to explore the possible mechanism of this transformation, which appears to involve a combination of two different pathways. Moreover this study provides insights into factors favoring and hindering Pd(i) dimer formation undesirable in catalysis.",

author = "Yaxu Liu and Voloshkin, {Vladislav A} and Thomas Scattolin and Luigi Cavallo and Busra Dereli and Cazin, {Catherine S. J.} and Nolan, {Steven P.}",

note = "KAUST Repository Item: Exported on 2021-05-03 Acknowledgements: We gratefully acknowledge VLAIO (SBO project CO2PERATE) and the Special Research Fund (BOF) of Ghent University. Funding of the iBOF project C3 (BOF20/IBF/010) is also gratefully acknowledge. Umicore AG is gratefully acknowledged for generous gifts of materials. Y. L. thanks the CSC for a PhD fellowship.",

year = "2021",

month = apr,

day = "28",

doi = "10.1039/d1dt00929j",

language = "English (US)",

volume = "50",

pages = "5420--5427",

journal = "Dalton transactions (Cambridge, England : 2003)",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Conversion of Pd(I) off-cycle species into highly efficient cross-coupling catalysts.

AU - Liu, Yaxu

AU - Voloshkin, Vladislav A

AU - Scattolin, Thomas

AU - Cavallo, Luigi

AU - Dereli, Busra

AU - Cazin, Catherine S. J.

AU - Nolan, Steven P.

N1 - KAUST Repository Item: Exported on 2021-05-03 Acknowledgements: We gratefully acknowledge VLAIO (SBO project CO2PERATE) and the Special Research Fund (BOF) of Ghent University. Funding of the iBOF project C3 (BOF20/IBF/010) is also gratefully acknowledge. Umicore AG is gratefully acknowledged for generous gifts of materials. Y. L. thanks the CSC for a PhD fellowship.

PY - 2021/4/28

Y1 - 2021/4/28

N2 - We report on the facile conversion of [Pd2(μ-Cl)(μ-η3-R-allyl)(NHC)2] complexes, which are commonly considered undesirable off-cycle species in cross-coupling reactions, into active [PdCl(μ-Cl)(NHC)]2 pre-catalysts. All reactions proceed under mild conditions (40 °C, 1-2 hours in acetone) using inexpensive HCl as both an oxidant and chloride source. DFT calculations were performed to explore the possible mechanism of this transformation, which appears to involve a combination of two different pathways. Moreover this study provides insights into factors favoring and hindering Pd(i) dimer formation undesirable in catalysis.

AB - We report on the facile conversion of [Pd2(μ-Cl)(μ-η3-R-allyl)(NHC)2] complexes, which are commonly considered undesirable off-cycle species in cross-coupling reactions, into active [PdCl(μ-Cl)(NHC)]2 pre-catalysts. All reactions proceed under mild conditions (40 °C, 1-2 hours in acetone) using inexpensive HCl as both an oxidant and chloride source. DFT calculations were performed to explore the possible mechanism of this transformation, which appears to involve a combination of two different pathways. Moreover this study provides insights into factors favoring and hindering Pd(i) dimer formation undesirable in catalysis.

UR - http://hdl.handle.net/10754/669033

UR - http://xlink.rsc.org/?DOI=D1DT00929J

U2 - 10.1039/d1dt00929j

DO - 10.1039/d1dt00929j

M3 - Article

C2 - 33908994

SN - 1477-9226

VL - 50

SP - 5420

EP - 5427

JO - Dalton transactions (Cambridge, England : 2003)

JF - Dalton transactions (Cambridge, England : 2003)

IS - 16

ER -

Conversion of Pd(I) off-cycle species into highly efficient cross-coupling catalysts.

Abstract

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