Electronic bond tuning with heterocyclic carbenes

Laura Falivene; Lucia Caporaso; Luigi Cavallo; Heiko Jacobsen

doi:10.1039/c3dt32923b

Electronic bond tuning with heterocyclic carbenes

Laura Falivene, Lucia Caporaso, Luigi Cavallo, Heiko Jacobsen

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2 Scopus citations

Abstract

We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

Original language	English (US)
Pages (from-to)	7281
Journal	Dalton Transactions
Volume	42
Issue number	20
DOIs	https://doi.org/10.1039/c3dt32923b
State	Published - 2013

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement no. CP-FP 211468-2 EUMET. L. C. thanks the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici, Italy.

ASJC Scopus subject areas

Inorganic Chemistry

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title = "Electronic bond tuning with heterocyclic carbenes",

abstract = "We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. {\textcopyright} 2013 The Royal Society of Chemistry.",

author = "Laura Falivene and Lucia Caporaso and Luigi Cavallo and Heiko Jacobsen",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement no. CP-FP 211468-2 EUMET. L. C. thanks the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici, Italy.",

year = "2013",

doi = "10.1039/c3dt32923b",

language = "English (US)",

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publisher = "Royal Society of Chemistry",

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T1 - Electronic bond tuning with heterocyclic carbenes

AU - Falivene, Laura

AU - Caporaso, Lucia

AU - Cavallo, Luigi

AU - Jacobsen, Heiko

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) under grant agreement no. CP-FP 211468-2 EUMET. L. C. thanks the HPC team of Enea for using the ENEA-GRID and the HPC facilities CRESCO in Portici, Italy.

PY - 2013

Y1 - 2013

N2 - We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

AB - We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

UR - http://hdl.handle.net/10754/562494

UR - http://xlink.rsc.org/?DOI=c3dt32923b

UR - http://www.scopus.com/inward/record.url?scp=84877260616&partnerID=8YFLogxK

U2 - 10.1039/c3dt32923b

DO - 10.1039/c3dt32923b

M3 - Article

SN - 1477-9226

VL - 42

SP - 7281

JO - Dalton Transactions

JF - Dalton Transactions

IS - 20

ER -

Electronic bond tuning with heterocyclic carbenes

Abstract

Bibliographical note

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